Phosphocholine-induced energy source shift alleviates mitochondrial dysfunction in lung cells caused by geospecific PM2.5 components.

Fine particulate matter (PM2.5) is globally recognized for its adverse implications on human health. Yet, remain limited the individual contribution of particular PM2.5 components to its toxicity, especially considering regional disparities. Moreover, prevention solutions for PM2.5-associated health effects are scarce. In the present study, we comprehensively characterized and compared the primary PM2.5 constituents and their altered metabolites from two locations: Taiyuan and Guangzhou. Analysis of year-long PM2.5 samples revealed 84 major components, encompassing organic carbon, elemental carbon, ions, metals, and organic chemicals. PM2.5 from Taiyuan exhibited higher contamination, associated health risks, dithiothreitol activity, and cytotoxicities than Guangzhou's counterpart. Applying metabolomics, BEAS-2B lung cells exposed to PM2.5 from both cities were screened for significant alterations. A correlation analysis revealed the metabolites altered by PM2.5 and the critical toxic PM2.5 components in both regions. Among the PM2.5-down-regulated metabolites, phosphocholine emerged as a promising intervention for PM2.5 cytotoxicities. Its supplementation effectively attenuated PM2.5-induced energy metabolism disorder and cell death via activating fatty acid oxidation and inhibiting Phospho1 expression. The highlighted toxic chemicals displayed combined toxicities, potentially counteracted by phosphocholine. Our study offered a promising functional metabolite to alleviate PM2.5-induced cellular disorder and provided insights into the geo-based variability in toxic PM2.5 components.

Unambiguous Analysis and Systematic Mapping of Oxygenated Aromatic Compounds in Atmospheric Aerosols Using Ultrahigh-Resolution Mass Spectrometry.

Compositional analysis of organic aerosols (OAs) at the molecular level has been a long-standing challenge in field and laboratory studies. In this work, we applied different extraction protocols to aerosol samples collected from the ambient atmosphere and biomass burning sources, followed by Orbitrap mass spectrometric analysis with a soft electrospray ionization source operating in both positive and negative ionization modes. To systematically map the distribution of mono- and dioxygenated aromatic compounds (referred to as aromatic CHO1 and CHO2 formulas) in OA, we developed a unique two-dimensional Kendrick mass defect (2D KMD) framework. Our analysis unveiled a total of (76, 64, 70) aromatic CHO1 formulas and (103, 110, 106) CHO2 formulas, corresponding to samples obtained from ambient air, rice straw burning, and sugarcane leaf burning, respectively. These results reveal a significant number of additional distinct formulas exclusively present in ambient samples, suggesting a significant chemical transformation of OAs in the atmosphere. The analytical approach can be further extended to incorporate multiple layers of 2D KMD, enabling systematic mapping of the unexplored chemical space for complex environmental samples.

Combustion-Derived Pollutants Linked with Kidney Disease in Low-Lying Flood-Affected Areas in the Balkans.

Tens of thousands of people in southern Europe suffer from Balkan endemic nephropathy (BEN), and four times as many are at risk. Incidental ingestion of aristolochic acids (AAs), stemming from the ubiquitousAristolochia clematitis(birthwort) weed in the region, leads to DNA adduct-induced toxicity in kidney cells, the primary cause of BEN. Numerous cofactors, including toxic organics and metals, have been investigated, but all have shown small contributions to the overall BEN relative to non-BEN village distribution gradients. Here, we reveal that combustion-derived pollutants from wood and coal burning in Serbia also contaminate arable soil and test as plausible causative factors of BEN. Using a GC-MS screening method, biomass-burning-derived furfural and coal-burning-derived medium-chain alkanes were detected in soil samples from BEN endemic areas levels at up to 63-times and 14-times higher, respectively, than in nonendemic areas. Significantly higher amounts were also detected in colocated wheat grains. Coexposure studies with cultured kidney cells showed that these pollutants enhance DNA adduct formation by AA, - the cause of AA nephrotoxicity and carcinogenicity. With the coincidence of birthwort-derived AAs and the widespread practice of biomass and coal burning for household cooking and heating purposes and agricultural burning in rural low-lying flood-affected areas in the Balkans, these results implicate combustion-derived pollutants in promoting the development of BEN.

Face Mask as a Versatile Sampling Device for the Assessment of Personal Exposure to 54 Toxic Compounds in Environmental Tobacco Smoke.

Exposure to environmental tobacco smoke (ETS), which contains hundreds of toxic compounds, significantly increases the risk of developing many human diseases, including lung cancer. The most common method of assessing personal exposure to ETS-borne toxicants is by sampling sidestream smoke generated by a smoking machine through a sorbent tube or filter, followed by solvent extraction and instrumental analysis. However, the ETS sampled may not truly represent the ETS in the ambient environment, due to complicating factors from the smoke released by the burning end of the cigarette and from the absorption of the chemicals in the respiratory tract of the smoker. In this study, we developed and validated an alternative air sampling method involving breathing through a face mask to simultaneously determine personal exposure to 54 ETS-borne compounds, including polycyclic aromatic hydrocarbons, aromatic amines, alkaloids, and phenolic compounds in real smoking scenarios. The newly developed method was used to evaluate the risk associated with exposure to ETS released from conventional cigarettes (CCs) and that from novel tobacco products such as e-cigarettes (ECs) and heated tobacco products (HTPs), with the observation of cancer risk associated with exposure to ETS released from CCs significantly higher than that from ECs and HTPs. It is anticipated that this method offers a convenient and sensitive way to collect samples for assessing the health impacts of ETS exposure.

Bayesian Inference Approach to Quantify Primary and Secondary Organic Carbon in Fine Particulate Matter Using Major Species Measurements.

The determination of primary organic carbon (POC) and secondary organic carbon (SOC) in fine particulate matter using ambient measurements is essential in atmospheric chemistry. A novel Bayesian inference (BI) approach is proposed to achieve such quantification using only major component measurement data and tested in two case studies. One case study composes of filter-based daily compositional data made in the Pearl River Delta region, China, during 2012, while the other uses online measurement data recorded at the Dianshan Lake monitoring site in Shanghai in wintertime 2019. Source-specific organic trace measurement data are available in both the cases so that positive matrix factorization (PMF) analysis is performed, where PMF-resolved POC and SOC are used as the best available reference values for model evaluation. Meanwhile, traditional techniques, i.e., minimum ratio value, minimum R squared, and multiple linear regression, are also employed and evaluated. For both the cases, the BI models have shown significant advantages in accurately estimating POC and SOC amounts over conventional methods. Further analysis suggests that using sulfate as the SOC tracer in BI model gives the best model performance. This methodological advance provides an improved and practical tool to derive POC and SOC levels for addressing PM-related environmental impacts.

Field Evidence for Asian Outflow and Fast Depletion of Total Gaseous Mercury in the Polluted Coastal Atmosphere.

Atmospheric mercury (Hg) cycling in polluted coastal atmosphere is complicated and not fully understood. Here, we present measurements of total gaseous mercury (TGM) monitored at a coastal mountaintop in Hong Kong downwind of mainland China. Sharp TGM peaks during cold front passages were frequently observed due to Asian pollution outflow with typical TGM/CO slopes of 6.8 ± 2.2 pg m-3 ppbv-1. Contrary to the daytime maximums of other air pollutants, TGM exhibited a distinct diurnal variation with a midday minimum. Moreover, we observed four cases of extremely fast TGM depletion after sunrise, during which TGM concentrations rapidly dipped to 0.3-0.6 ng m-3 accompanied by other pollutants on the rise. Simulated meteorological fields revealed that morning upslope flow transporting anthropogenically polluted but TGM-depleted air masses from the mixed layer caused morning TGM depletion at the mountaintop location. The TGM-depleted air masses were hypothesized to result mainly from fast photooxidation of Hg after sunrise with minor contributions from dry deposition (5.0%) and nocturnal oxidation (0.6%). A bromine-induced two-step oxidation mechanism involving abundant pollutants (NO2, O3, etc.) was estimated to play a dominant role, contributing 55%-60% of depleted TGM and requiring 0.20-0.26 pptv Br, an amount potentially available through sea salt aerosol debromination. Our findings suggest significant effects of the interaction between anthropogenic pollution and marine halogen chemistry on atmospheric Hg cycling in the coastal areas.

Important Roles and Formation of Atmospheric Organosulfates in Marine Organic Aerosols: Influence of Phytoplankton Emissions and Anthropogenic Pollutants.

Organosulfates (OSs) could be potentially important compounds in marine organic aerosols, while their formation in marine atmospheres is far from clear due to a lack of cruise observations. In this work, shipboard atmospheric observations were conducted over the Yellow Sea and Bohai Sea to investigate the abundance and formation of biogenic isoprene/monoterpene-OSs in marine aerosols. The quantified OSs and NOSs accounted for 0.04-6.9% of marine organic aerosols and were 0.07-2.2% of the non-sea-salt (nss) sulfate in terms of sulfur content. Isoprene-related (nitrooxy-)OSs occupied 27-87% of the total quantified OSs, following the abundance order of summer > autumn > spring or winter. This order was driven by the marine phytoplankton biomass and sea surface temperature (SST), which controlled the seawater and atmospheric isoprene concentration levels. Under the severe impacts of anthropogenic pollutants from the East Asia continent in winter, monoterpene nitrooxy-OSs, generated with NOx involved in, increased to 34.4 ± 35.5 ng/m3 and contributed 68% of the quantified (nitrooxy-)OSs. Our results highlight the notable roles of biogenic OSs in marine organic aerosols over regions with high biological activity and high SST. The formation of biogenic OSs and their roles in altering marine aerosol properties calls for elaboration through cruise observations in different marine environments.

Polyurethane Foam Face Masks as a Dosimeter for Quantifying Personal Exposure to Airborne Volatile and Semi-Volatile Organic Compounds.

Airborne volatile organic compounds (VOCs) and semi-volatile organic compounds (SVOCs) are commonly quantitated by collecting the analytes on solid sorbent tubes or passive air samplers, followed by solvent extraction and instrumental analysis, or by grab bag/canister measurements. We report herein a user-friendly sampling method by breathing through polyurethane foam (PUF) face masks to collect airborne VOCs and SVOCs for chemical analysis. Specifically, dibasic esters, phthalate esters, polycyclic aromatic hydrocarbons, linalool, and nicotine trapped on PUF masks were quantitated by gas chromatography-mass spectrometry analysis as model VOCs and SVOCs. Results showed that the amount of these model VOCs and SVOCs trapped on PUF masks is proportional to the exposure duration. After cross-validation by parallel sampling using XAD-2 packed sorbent tubes, the method was used to quantitate VOCs and SVOCs in a variety of indoor and outdoor environments with varying air concentrations of analytes, temperature, humidity, and wind speed. Because air pollution is considered a major cause of many human diseases and premature deaths and the developed PUF mask sampling method showed high trapping efficiencies for both VOCs and SVOCs, it is believed that the developed sampling method will find wide application in assessing air pollution-associated disease risks with possible extension to more classes of VOCs and SVOCs when coupled with suitable instrumental detection methods.

Modeling Secondary Organic Aerosol Tracers and Tracer-to-SOA Ratios for Monoterpenes and Sesquiterpenes Using a Chemical Transport Model.

The community multiscale air quality (CMAQ) model was modified to simulate secondary organic aerosol (SOA) formation from five explicit (α-pinene, ß-pinene, d-limonene, Δ3-carene, and sabinene) and one lumped monoterpene (MT) species and sesquiterpenes (SQTs). The contribution of each oxidation pathway [including OH, O3, NO3, and O(3P)] was explicitly tracked in the SOA module. Three MT SOA tracers (pinic acid, PA; pinonic acid, PNA; and 3-methyl-1,2,3-butanetricarboxylic acid, MBTCA) and one SQT SOA tracer (ß-caryophyllinic acid, BCARYA) were modeled to assess the tracer-to-SOA ratios (fSOA) for ambient SOA estimation. Good model performance for BCARYA and MBTCA and reasonable agreement between model predictions and observations of PA and PNA were achieved. The modeled daily fSOA showed significant variations, suggesting that using the chamber-derived constant fSOA could lead to large errors in estimating terpene SOA. Among the four tracers, MBTCA and BCARYA were more appropriate for tracking MT and SQT SOA due to their nonvolatility. Their fSOA values mainly depend on the organic aerosol loading and could be approximated using simple power-law equations. In addition, equations directly linking the tracer concentrations to the corresponding SOA concentrations were proposed and could lead to good SOA estimations. This work provides new insights into the formation of the key MT and SQT SOA tracers and would allow better assessments of the biogenic emissions to regional and global aerosol burden.

Hourly organic tracers-based source apportionment of PM2.5 before and during the Covid-19 lockdown in suburban Shanghai, China: Insights into regional transport influences and response to urban emission reductions.

During the Covid-19 outbreak, strict lockdown measures led to notable reductions in transportation-related emissions and significantly altered atmospheric pollution characteristics in urban and suburban areas. In this work, we compare comprehensive online measurements of PM2.5 major components and organic molecular markers in a suburban location in Shanghai, China before lockdown (Dec. 28, 2019 to Jan. 23, 2020) and during lockdown (Jan. 24 to Feb. 9, 2020). The NOx levels declined sharply by 59% from 44 to 18 ppb during the lockdown, while O3 rose two times higher to 42 ppb. The PM2.5 level dropped from 64 to 49 µg m-3 (-24%). The major components all showed reductions, with the reduction of nitrate most prominent at -58%, followed by organics at -19%, and sulfate at -17%. Positive matrix factorization analysis identifies fourteen source factors, including nine primary sources and five secondary sources. The secondary sources consist of sulfate-rich factor, nitrate-rich factor, and three secondary organic aerosol (SOA) factors, with SOA_I being anthropogenic SOA, SOA_II associated with later generation products of organic oxidation, and SOA_III being biogenic SOA. The combined secondary sources contributed to 69% and 63% (40 and 22 µg m-3) of PM2.5 before and during lockdown, respectively, among which the reductions in the nitrate-rich (-55%) factor was the most prominent. Among primary sources, large reductions (>80%) were observed in contributions from industrial, cooking, and vehicle emissions. Unlike some studies reporting that the restriction during the Covid-19 resulted in enhanced secondary sulfate and SOA formation, we observed decreases in both secondary inorganic and SOA formation despite the overall elevated oxidizing capacity in the suburban site. Our results indicate that the formation change in secondary inorganic and organic compounds in response to substantial reductions in urban primary precursors are different for urban and suburban environments.

Ammonia emission control in China would mitigate haze pollution and nitrogen deposition, but worsen acid rain.

China has been experiencing fine particle (i.e., aerodynamic diameters ≤ 2.5 µm; PM2.5) pollution and acid rain in recent decades, which exert adverse impacts on human health and the ecosystem. Recently, ammonia (i.e., NH3) emission reduction has been proposed as a strategic option to mitigate haze pollution. However, atmospheric NH3 is also closely bound to nitrogen deposition and acid rain, and comprehensive impacts of NH3 emission control are still poorly understood in China. In this study, by integrating a chemical transport model with a high-resolution NH3 emission inventory, we find that NH3 emission abatement can mitigate PM2.5 pollution and nitrogen deposition but would worsen acid rain in China. Quantitatively, a 50% reduction in NH3 emissions achievable by improving agricultural management, along with a targeted emission reduction (15%) for sulfur dioxide and nitrogen oxides, can alleviate PM2.5 pollution by 11-17% primarily by suppressing ammonium nitrate formation. Meanwhile, nitrogen deposition is estimated to decrease by 34%, with the area exceeding the critical load shrinking from 17% to 9% of China's terrestrial land. Nevertheless, this NH3 reduction would significantly aggravate precipitation acidification, with a decrease of as much as 1.0 unit in rainfall pH and a corresponding substantial increase in areas with heavy acid rain. An economic evaluation demonstrates that the worsened acid rain would partly offset the total economic benefit from improved air quality and less nitrogen deposition. After considering the costs of abatement options, we propose a region-specific strategy for multipollutant controls that will benefit human and ecosystem health.

Polyurethane-Based Face Mask as a Sampling Device for Environmental Tobacco Smoke.

Environmental tobacco smoke (ETS), also known as secondhand smoking, contains human carcinogens associated with the development of many human diseases, including stroke, heart disease, leukemia, and lung cancer. Due to these adverse health effects, a sensitive and selective method is crucial for assessing the health impacts of ETS. While current methods to evaluate ETS exposure are either invasive or nonspecific and insensitive, in this study, we assessed the use of polyurethane foam face masks as a sampling medium to collect tobacco smoke-specific nicotine and nitrosamines for estimating personal exposure to ETS. This method was used in conjunction with tandem mass spectrometry coupled with isotope-dilution detection. After validation by comparison with the National Institute for Occupational Safety and Health standard method (NIOSH 2551) for nicotine, we quantitated ETS exposure in indoor and outdoor environments. The analysis shows the applicability of the method for monitoring nicotine down to ∼0.20 mg/m3 near an outdoor smoking hotspot and up to ∼5.2 mg/m3 in a room with burning cigarettes, all with a time resolution as short as 5 min. In comparison with the NIOSH method, the newly developed method is convenient, inexpensive, and does not require a personal sampling pump, thus can facilitate large-scale ETS exposure monitoring.

Tracer-based characterization of source variations of PM2.5 and organic carbon in Shanghai influenced by the COVID-19 lockdown.

Air quality in megacities is significantly impacted by emissions from vehicles and other urban-scale human activities. Amid the outbreak of Coronavirus (COVID-19) in January 2020, strict policies were in place to restrict people's movement, bringing about steep reductions in pollution activities and notably lower ambient concentrations of primary pollutants. In this study, we report hourly measurements of fine particulate matter (i.e., PM2.5) and its comprehensive chemical speciation, including elemental and molecular source tracers, at an urban site in Shanghai spanning a period before the lockdown restriction (BR) (1 to 23 Jan. 2020) and during the restriction (DR) (24 Jan. to 9 Feb. 2020). The overall PM2.5 was reduced by 27% from 56.2 ± 40.9 (BR) to 41.1 ± 25.3 µg m-3 (DR) and the organic carbon (OC) in PM2.5 was similar, averaged at 5.45 ± 2.37 (BR) and 5.42 ± 1.75 µgC m-3 (DR). Reduction in nitrate was prominent, from 18.1 (BR) to 9.2 µg m-3 (DR), accounting for most of the PM2.5 decrease. Source analysis of PM2.5 using positive matrix factorization modeling of comprehensive chemical composition, resolved nine primary source factors and five secondary source factors. The quantitative source analysis confirms reduced contributions from primary sources affected by COVID-19, with vehicular emissions showing the largest drop, from 4.6 (BR) to 0.61 µg m-3 (DR) and the percentage change (-87%) in par with vehicle traffic volume and fuel sale statistics (-60% to -90%). In the same time period, secondary sources are revealed to vary in response to precursor reductions from the lockdown, with two sources showing consistent enhancement while the other three showing reductions, highlighting the complexity in secondary organic aerosol formation and the nonlinear response to broad primary precursor pollutants. The combined contribution from the two secondary sources to PM2.5 increased from 7.3 ± 6.6 (BR) to 14.8 ± 9.3 µg m-3 (DR), partially offsetting the reductions from primary sources and nitrate while their increased contribution to OC, from 1.6 ± 1.4 (BR) to 3.2 ± 2.0 µgC m-3 (DR), almost offset the decrease coming from the primary sources. Results from this work underscore challenges in predicting the benefits to PM2.5 improvement from emission reductions of common urban primary sources.

Chemical Synthesis of Multifunctional Air Pollutants: Terpene-Derived Nitrooxy Organosulfates.

Nitrooxy organosulfates derived from terpenes (NOSTP) represent an important class of products formed between anthropogenic pollution (e.g., SO2 and NOx) and natural emissions. NOSTP compounds have been consistently detected in atmospheric environments under varying urban influences. Their chemical linkages to both anthroposphere and biosphere make them valuable markers for tracking anthroposphere-biosphere interactions. However, their quantification, formation, and transformation kinetics in atmospheric aerosols are hindered due to the lack of NOSTP standards. In this work, we developed two routes for the first concise chemical synthesis of eight NOSTP from terpenes including α-pinene, ß-pinene, limonene, limonaketone, and ß-caryophyllene. Subsequently, six of the synthesized NOSTP were for the first time positively identified in ambient aerosol samples, clarifying certain misidentifications in previous studies. More significantly, the availability of authentic standards allows irrefutable observation of three carbon skeleton-rearranged NOSTP, two derived from α-pinene, and one derived from ß-caryophyllene, revealing the occurrence of previously unrecognized transformation pathways in the formation of NOSTP. Two synthesized NOSTP from ß-pinene and limonene could not be detected, likely due to rapid hydrolysis of their immediate hydroxynitrate precursors outcompeting sulfation. Such mechanistic evidence is valuable in understanding the atmospheric chemistry of NOSTP and related compounds. This work demonstrates the usefulness of authentic standards in probing the NOSTP formation mechanisms in the atmosphere. Comparison of NOSTP ambient samples collected from four Chinese cities in two winter months indicates that anthropogenic chemical factors could outcompete terpene emissions in the formation of NOSTP.

On the Flip Side of Mask Wearing: Increased Exposure to Volatile Organic Compounds and a Risk-Reducing Solution.

Surgical masks have been worn by the public worldwide during the COVID-19 pandemic, yet hazardous chemicals in the petroleum-derived polymer layer of masks are currently ignored and unregulated. These organic compounds pose potential health risks to the mask wearer through dermal contact or inhalation. Here, we show that surgical masks from around the world are loaded with semivolatile and volatile organic compounds (VOCs), including alkanes, polycyclic aromatic hydrocarbons (PAHs), phthalate esters, and reactive carbonyls at ng to µg/mask levels. Naphthalene was the most abundant mask-borne PAH, accounting for over 80% of total PAH levels; acrolein, a mutagenic carbonyl, was detected in most of the mask samples, and di(2-ethylhexyl) phthalate, an androgen antagonist, was detected in one-third of the samples. Furthermore, there is large mask-to-mask variability of the residue VOCs, revealing the uneven quality of masks. We confirm that masks containing more residue VOCs lead to significantly higher exposure levels and associated disease risks to the wearer, which should warrant the attention of the general public and regulatory agencies. We find that heating the masks at 50 °C for as short as 60 min lowers the total VOC content by up to 80%, providing a simple method to limit our exposure to mask-borne VOCs.

Fabric Masks as a Personal Dosimeter for Quantifying Exposure to Airborne Polycyclic Aromatic Hydrocarbons.

In this study, we assessed the feasibility of using ordinary face masks as a sampling means to collect airborne polycyclic aromatic hydrocarbons (PAHs). Nonwoven fabric masks can trap three-ring or larger PAHs at a high efficiency (>70%) and naphthalene at ∼17%. The sampling method is quantitative as confirmed by comparison with the standard method of the National Institute for Occupational Safety and Health. In conjunction with sensitive fluorescence detection, the method was applied to quantify nine airborne PAHs in a range of indoor and outdoor environments. Wearing the mask for 2 h allowed quantification of individual PAHs as low as 0.07 ng/m3. The demonstration shows applicability of the method in monitoring PAHs down to ∼30-80 ng/m3 in university office and laboratory settings and up to ∼900 ng/m3 in an incense-burning temple. Compared with traditional filter-/sorbent tube-based approaches, which require a sampling pump, our new method is simple, convenient, and inexpensive. More importantly, it closely tracks human exposure down to the individual level, thus having great potential to facilitate routine occupational exposure monitoring and large-scale surveillance of PAH concentrations in indoor and outdoor environments.

Simultaneous Determination of Aerosol Inorganic and Organic Nitrogen by Thermal Evolution and Chemiluminescence Detection.

Inorganic nitrogen (IN) and organic nitrogen (ON) molecules constitute a significant part of atmospheric aerosol. Unlike IN, the total ON quantity remains largely unquantified due to a lack of a simple and direct measurement method. This analytical deficiency hinders the quantitative assessment of the various environmental and health effect impacts by aerosol ON. In this work, we developed an analyzer system that utilizes programmed thermal evolution of carbonaceous and nitrogenous aerosols and chemiluminescence detection coupled with the multivariate curve resolution data treatment to achieve simultaneous quantification of IN and ON. The system is capable of detecting IN and ON as low as 96 ng N per sample on a small filter aliquot (1 cm2) without any pretreatment. This method breakthrough opens the door to quantifying an important pool of aerosol N that was analytically inaccessible in the past and holds the promise to quantifying IN and ON in other environmental samples. As a demonstration, quantification of aerosol ON at an urban site in Hong Kong, China, in samples spanning over a year reveals ON constituting a significant fraction (9-52%) of the total aerosol nitrogen and having major source origins in both secondary formation and primary emissions.

Estimation of Aromatic Secondary Organic Aerosol Using a Molecular Tracer-A Chemical Transport Model Assessment.

A modified community multiscale air quality model, which can simulate the regional distributions of 2,3-dihydroxy-4-oxopentanoic acid (DHOPA), a marker species for monoaromatic secondary organic aerosol (SOA), was applied to assess the applicability of using the DHOPA to aromatic SOA mass ratio (fSOA) from smog chamber experiments to estimate aromatic SOA during a three-week wintertime air quality campaign in urban Shanghai. The modeled daily DHOPA concentrations based on the chamber-derived mass yields agree well with the organic marker field measurements (R = 0.79; MFB = 0.152; and MFE = 0.440). Two-thirds of the DHOPA are from the oxidation of ARO1 (lumped less-reactive aromatic species; mostly toluene), with the rest from ARO2 (lumped more-reactive aromatic species; mostly xylenes). Modeled DHOPA is mainly in the particle phase under ambient organic aerosol (OA) loading but could exhibit significant gas-particle partitioning when a higher estimation of the DHOPA vapor pressure is used. The modeled fSOA shows a strong dependence on the OA loading when only semivolatile aromatic SOA components are included in the fSOA calculations. However, this OA dependence becomes weaker when non-volatile oligomers and dicarbonyl SOA products are considered. A constant fSOA value of ∼0.002 is determined when all aromatic SOA components are included, which is a factor of 2 smaller than the commonly applied chamber-based fSOA value of 0.004 for toluene. This model-derived fSOA value does not show much spatial variation and is not sensitive to alternative estimates of DHOPA vapor pressures and SOA yields, and thus provides an appropriate scaling factor to assess aromatic SOA from DHOPA measurements. This result helps refine the quantification of SOA attributable to monoaromatic hydrocarbons in urban environments and thereby facilitates the evaluation of control measures targeting these specific precursors.

Comparative Assessment of Cooking Emission Contributions to Urban Organic Aerosol Using Online Molecular Tracers and Aerosol Mass Spectrometry Measurements.

Cooking organic aerosol (COA) is an important source of particulate pollutants in urbanized regions. Yet, the diversity and complexity of COA components make direct identification and quantification of COA difficult. In this study, we conducted collocated OA measurements with an aerosol mass spectrometer (AMS) and a thermal desorption aerosol gas chromatography-mass spectrometer (TAG) in Shanghai. Cooking molecular tracers (e.g., C18 fatty acids, azelaic acid) measured by TAG provide unambiguous source information for evaluating the tracer ion (C6H10O+, m/z 98) used for identification and apportionment of COA in AMS analysis. Based on the collocated AMS and TAG measurements, two COA factors, namely, a primary COA (PCOA) and an oxygenated COA (OCOA) produced from rapid oxygenation of freshly emitted PCOA, were identified. Criteria for identifying COA factors from AMS analysis with different oxygenation levels are proposed, i.e., characteristic mass spectra, temporal variations, etc. Furthermore, two positive matrix factorization approaches, namely, AMS-PMF and the molecular marker (MM)-PMF, were compared for COA quantification, where high consistency was found with the contribution of COA to total PM2.5 mass estimated to be 9 ± 7% by AMS-PMF and 6 ± 5% by the MM-PMF. Our study highlights the important impacts of cooking activities on air quality in urban areas. We also demonstrate the advantage of conducting collocated measurements using multiple high time resolution mass spectrometric techniques in advancing our understanding of atmospheric OA chemistry and improving the accuracy of source apportionment.

Impacts of Chemical Degradation on the Global Budget of Atmospheric Levoglucosan and Its Use As a Biomass Burning Tracer.

Levoglucosan has been widely used to quantitatively assess biomass burning's contribution to ambient aerosols, but previous such assessments have not accounted for levoglucosan's degradation in the atmosphere. We develop the first global simulation of atmospheric levoglucosan, explicitly accounting for its chemical degradation, to evaluate the impacts on levoglucosan's use in quantitative aerosol source apportionment. Levoglucosan is emitted into the atmosphere from the burning of plant matter in open fires (1.7 Tg yr-1) and as biofuels (2.1 Tg yr-1). Sinks of atmospheric levoglucosan include aqueous-phase oxidation (2.9 Tg yr-1), heterogeneous oxidation (0.16 Tg yr-1), gas-phase oxidation (1.4 × 10-4 Tg yr-1), and dry and wet deposition (0.27 and 0.43 Tg yr -1). The global atmospheric burden of levoglucosan is 19 Gg with a lifetime of 1.8 days. Observations show a sharp decline in levoglucosan's concentrations and its relative abundance to organic carbon aerosol (OC) and particulate K+ from near-source to remote sites. We show that such features can only be reproduced when levoglucosan's chemical degradation is included in the model. Using model results, we develop statistical parametrizations to account for the atmospheric degradation in levoglucosan measurements, improving their use for quantitative aerosol source apportionment.