Reactive aldehyde chemistry explains the missing source of hydroxyl radicals.

Hydroxyl radicals (OH) determine the tropospheric self-cleansing capacity, thus regulating air quality and climate. However, the state-of-the-art mechanisms still underestimate OH at low nitrogen oxide and high volatile organic compound regimes even considering the latest isoprene chemistry. Here we propose that the reactive aldehyde chemistry, especially the autoxidation of carbonyl organic peroxy radicals (R(CO)O2) derived from higher aldehydes, is a noteworthy OH regeneration mechanism that overwhelms the contribution of the isoprene autoxidation, the latter has been proved to largely contribute to the missing OH source under high isoprene condition. As diagnosed by the quantum chemical calculations, the R(CO)O2 radicals undergo fast H-migration to produce unsaturated hydroperoxyl-carbonyls that generate OH through rapid photolysis. This chemistry could explain almost all unknown OH sources in areas rich in both natural and anthropogenic emissions in the warm seasons, and may increasingly impact the global self-cleansing capacity in a future low nitrogen oxide society under carbon neutrality scenarios.

Revisiting the Ultraviolet Absorption Cross Section of Gaseous Nitrous Acid (HONO): New Insights for Atmospheric HONO Budget.

Nitrous acid (HONO) is an important source of hydroxyl radicals (OH) in the atmosphere. Precise determination of the absolute ultraviolet (UV) absorption cross section of gaseous HONO lays the basis for the accurate measurement of its concentration by optical methods and the estimation of HONO loss rate through photolysis. In this study, we performed a series of laboratory and field intercomparison experiments for HONO measurement between striping coil-liquid waveguide capillary cell (SC-LWCC) photometry and incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). Specified HONO concentrations prepared by an ultrapure standard HONO source were utilized for laboratory intercomparisons. Results show a consistent ∼22% negative bias in measurements of the IBBCEAS compared with a SC-LWCC photometer. It is confirmed that the discrepancies occurring between these techniques are associated with the overestimation of the absolute UV absorption cross sections through careful analysis of possible uncertainties. We quantified the absorption cross section of gaseous HONO (360-390 nm) utilizing a custom-built IBBCEAS instrument, and the results were found to be 22-34% lower than the previously published absorption cross sections widely used in HONO concentration retrieval and atmospheric chemical transport models (CTMs). This suggests that the HONO concentrations retrieved by optical methods based on absolute absorption cross sections may have been underestimated by over 20%. Plus, the daytime loss rate and unidentified sources of HONO may also have evidently been overestimated in pre-existing studies. In summary, our findings underscore the significance of revisiting the absolute absorption cross section of HONO and the re-evaluation of the previously reported HONO budgets.

Impact of aerosol in-situ peroxide formations induced by metal complexes on atmospheric H2O2 budgets.

Hydrogen peroxide (H2O2), hydroxyl radicals (OH), hydroperoxyl (HO2), and superoxide (O2-) radicals interacting with aerosol particles significantly affect the atmospheric pollutant budgets. A multiphase chemical kinetic box model (PKU-MARK), including the multiphase processes of transition metal ions (TMI) and their organic complexes (TMI-OrC), was built to numerically drive H2O2 chemical behaviors in the aerosol particle liquid phase using observational data obtained from a field campaign in rural China. Instead of relying on fixed uptake coefficient values, a thorough simulation of multiphase H2O2 chemistry was performed. In the aerosol liquid phase, light-driven TMI-OrC reactions promote OH, HO2/O2-, and H2O2 recycling and spontaneous regenerations. The in-situ generated aerosol H2O2 would offset gas-phase H2O2 molecular transfer into the aerosol bulk phase and promote the gas-phase level. When combined with the multiphase loss and in-situ aerosol generation involving TMI-OrC mechanism, the HULIS-Mode significantly improves the consistency between modeled and measured gas-phase H2O2 levels. Aerosol liquid phase could be a pivotal potential source of aqueous H2O2 and influence the multiphase budgets. Our work highlights the intricate and significant effects of aerosol TMI and TMI-OrC interactions on the multiphase partitioning of H2O2 when assessing atmospheric oxidant capacity.

Field observations and quantifications of atmospheric formaldehyde partitioning in gaseous and particulate phases.

Formaldehyde (HCHO) can possibly be taken by atmospheric particles due to its moderate solubility. Although previous model studies have proposed that uptake by particles was a large sink for HCHO, direct observation of HCHO partitioning and estimation of HCHO uptake coefficient (γ) for tropospheric conditions are still limited. In this work, online measurements of gaseous HCHO (HCHOg) and particulate HCHO (HCHOp) were carried out simultaneously at an urban site in Beijing in winter and spring. The results indicated that the average concentrations of HCHOp ranged from 0.15 to 0.4 µg m-3, accounting for 1.2% to 10% of the total HCHO (i.e., HCHOg + HCHOp). The median values of estimated γ based on the measured data were in the range of about 1.09 ∗ 10-5-2.42 ∗ 10-4, with lower values during PM2.5 pollution episodes. Besides, the pH and liquid water content of aerosols that are mainly determined by ambient relative humidity (RH) and inorganic salt composition were identified as the main influencing factors of γ. We propose that the HCHO uptake process was mainly driven by hydrone and hydrogen ions in particles.

Links between the optical properties and chemical compositions of brown carbon chromophores in different environments: Contributions and formation of functionalized aromatic compounds.

Links between the optical properties and chemical compositions of brown carbon (BrC) are poorly understood because of the complexity of BrC chromophores. We conducted field studies simultaneously at both vehicle-influenced site and biomass burning-affected site in China in polluted winter. The chemical compositions and light absorption values of functionalized aromatic compounds, including phenyl aldehyde, phenyl acid, and nitroaromatic compounds, were measured. P-phthalic acid, nitrophenols and nitrocatechols were dominant BrC species, accounting for over 50% of the concentration of identified chromophores. Nitrophenols and nitrocatechols contributed more than 50% of the identified BrC absorbance between 300 and 400 nm. Oxidation of biomass burning-related products (e.g., pyrocatechol and methylcatechols) and anthropogenic volatile organic compounds (e.g., benzene and toluene) generated similar BrC chromophores, implying that these functionalized aromatic compounds play an important role in both environments. Compared with the biomass burning-affected site (22%), functionalized aromatic compounds at vehicle-influenced site accounted for a higher percentage of BrC absorption (25%). This research improves our understanding of the links between optical properties and composition of BrC, and the difference between BrC chromophores from BB-influenced area and vehicle-affected area under polluted atmospheric conditions.

Observations and modeling of OH and HO2 radicals in Chengdu, China in summer 2019.

This study reports on the first continuous measurements of ambient OH and HO2 radicals at a suburban site in Chengdu, Southwest China, which were collected during 2019 as part of a comprehensive field campaign 'CompreHensive field experiment to explOre the photochemical Ozone formation mechaniSm in summEr - 2019 (CHOOSE-2019)'. The mean concentrations (11:00-15:00) of the observed OH and HO2 radicals were 9.5 × 106 and 9.0 × 108 cm-3, respectively. To investigate the state-of-the-art chemical mechanism of radical, closure experiments were conducted with a box model, in which the RACM2 mechanism updated with the latest isoprene chemistry (RACM2-LIM1) was used. In the base run, OH radicals were underestimated by the model for the low-NO regime, which was likely due to the missing OH recycling. However, good agreement between the observed and modeled OH concentrations was achieved when an additional species X (equivalent to 0.25 ppb of NO mixing ratio) from one new OH regeneration cycle (RO2 + X â†’ HO2, HO2 + X â†’ OH) was added into the model. Additionally, in the base run, the model could reproduce the observed HO2 concentrations. Discrepancies in the observed and modeled HO2 concentrations were found in the sensitivity runs with HO2 heterogeneous uptake, indicating that the impact of the uptake may be less significant in Chengdu because of the relatively low aerosol concentrations. The ROx (= OH + HO2 + RO2) primary source was dominated by photolysis reactions, in which HONO, O3, and HCHO photolysis accounted for 34%, 19%, and 23% during the daytime, respectively. The efficiency of radical cycling was quantified by the radical chain length, which was determined by the NO to NO2 ratio successfully. The parameterization of the radical chain length may be very useful for the further determinations of radical recycling.

Elucidating the effect of HONO on O3 pollution by a case study in southwest China.

Photolysis of nitrous acid (HONO) is one of the major sources for atmospheric hydroxyl radicals (OH), playing significant role in initiating tropospheric photochemical reactions for ozone (O3) production. However, scarce field investigations were conducted to elucidate this effect. In this study, a field campaign was conducted at a suburban site in southwest China. The whole observation was classified into three periods based on O3 levels and data coverage: the serious O3 pollution period (Aug 13-18 as P1), the O3 pollution period (Aug 22-28 as P2) and the clean period (Sep 3-12 as P3), with average O3 peak values of 96 ppb, 82 ppb and 44 ppb, respectively. There was no significant difference of the levels of O3 precursors (VOCs and NOx) between P1 and P2, and thus the evident elevation of OH peak values in P1 was suspected to be the most possible explanation for the higher O3 peak values. Considering the larger contribution of HONO photolysis to HOX primary production than photolysis of HCHO, O3 and ozonolysis of Alkenes, sensitivity tests of HONO reduction on O3 production rate in P1 are conducted by a 0-dimension model. Reduced HONO concentration effectively slows the O3 production in the morning, and such effect correlates with the calculated production rate of OH radicals from HONO photolysis. Higher HONO level supplying for OH radical initiation in the early morning might be the main reason for the higher O3 peak values in P1, which explained the correlation (R2 = 0.51) between average O3 value during daytime (10:00-19:00 LT) and average HONO value during early morning (00:00-05:00 LT). For nighttime accumulation, a suitable range of relative humidity that favored NO2 conversion within P1 was assumed to be the reason for the higher HONO concentration in the following early morning which promoted O3 peak values.

High Gaseous Nitrous Acid (HONO) Emissions from Light-Duty Diesel Vehicles.

Nitrous acid (HONO) plays an important role in the budget of hydroxyl radical (•OH) in the atmosphere. Vehicular emissions are a crucial primary source of atmospheric HONO, yet remain poorly investigated, especially for diesel trucks. In this study, we developed a novel portable online vehicular HONO exhaust measurement system featuring an innovative dilution technique. Using this system coupled with a chassis dynamometer, we for the first time investigated the HONO emission characteristics of 17 light-duty diesel trucks (LDDTs) and 16 light-duty gasoline vehicles in China. Emissions of HONO from LDDTs were found to be significantly higher than previous studies and gasoline vehicles tested in this study. The HONO emission factors of LDDTs decrease significantly with stringent control standards: 1.85 ± 1.17, 0.59 ± 0.25, and 0.15 ± 0.14 g/kg for China III, China IV, and China V, respectively. In addition, we found poor correlations between HONO and NOx emissions, which indicate that using the ratio of HONO to NOx emissions to infer HONO emissions might lead to high uncertainty of HONO source budget in previous studies. Lastly, the HONO emissions are found to be influenced by driving conditions, highlighting the importance of conducting on-road measurements of HONO emissions under real-world driving conditions. More direct measurements of the HONO emissions are needed to improve the understanding of the HONO emissions from mobile and other primary sources.

Field Determination of Nitrate Formation Pathway in Winter Beijing.

Particulate nitrate (pNO3-) has often been found to be the major component of fine particles in urban air-sheds in China, the United States, and Europe during winter haze episodes in recent years. However, there is a lack of knowledge regarding the experimentally determined contribution of different chemical pathways to the formation of pNO3-. Here, for the first time, we combine ground and tall-tower observations to quantify the chemical formation of pNO3- using observationally constrained model approach based on direct observations of OH and N2O5 for the urban air-shed. We find that the gas-phase oxidation pathway (OH+NO2) during the daytime is the dominant channel over the nocturnal uptake of N2O5 during pollution episodes, with percentages of 74% in urban areas and 76% in suburban areas. This is quite different from previous studies in some regions of the US, in which the uptake of N2O5 was concluded to account for a larger contribution in winter. These results indicate that the driving factor of nitrate pollution in Beijing and different regions of the US is different, as are the mitigation strategies for particulate nitrate.

Profiling Aerosol Liquid Water Content Using a Polarization Lidar.

Aerosol liquid water content (ALWC) plays fundamental roles in atmospheric radiation and chemical processes. However, there is little information about ALWC vertical distribution due to the lack of sufficient measurement. In this study, a novel method to retrieve ALWC using a polarization lidar is proposed. By analyzing lidar measurement combined with in situ chemical composition measurements at the surface, the particle linear depolarization ratio δp is found to be well correlated with the liquid water mass fraction. The method is built upon a valid relationship between δp and the ratio of ALWC to the particle backscatter coefficient. ALWC can be retrieved with a relative error of 30% with this method. A case study shows that the ALWC in upper levels of the boundary layer may be different from that at the ground, suggesting the importance of measuring ALWC vertical profiles during haze episodes. The study proves that polarization lidars have the potential to retrieve vertical distributions of ALWC which will benefit studies on haze formation.

Fast Photochemistry in Wintertime Haze: Consequences for Pollution Mitigation Strategies.

In contrast to summer smog, the contribution of photochemistry to the formation of winter haze in northern mid-to-high latitude is generally assumed to be minor due to reduced solar UV and water vapor concentrations. Our comprehensive observations of atmospheric radicals and relevant parameters during several haze events in winter 2016 Beijing, however, reveal surprisingly high hydroxyl radical oxidation rates up to 15 ppbv/h, which is comparable to the high values reported in summer photochemical smog and is two to three times larger than those determined in previous observations during winter in Birmingham (Heard et al. Geophys. Res. Lett. 2004, 31, (18)), Tokyo (Kanaya et al. J. Geophys. Res.: Atmos. 2007, 112, (D21)), and New York (Ren et al. Atmos. Environ. 2006, 40, 252-263). The active photochemistry facilitates the production of secondary pollutants. It is mainly initiated by the photolysis of nitrous acid and ozonolysis of olefins and maintained by an extremely efficiently radical cycling process driven by nitric oxide. This boosted radical recycling generates fast photochemical ozone production rates that are again comparable to those during summer photochemical smog. The formation of ozone, however, is currently masked by its efficient chemical removal by nitrogen oxides contributing to the high level of wintertime particles. The future emission regulations, such as the reduction of nitrogen oxide emissions, therefore are facing the challenge of reducing haze and avoiding an increase in ozone pollution at the same time. Efficient control strategies to mitigate winter haze in Beijing may require measures similar as implemented to avoid photochemical smog in summer.

A Comprehensive Model Test of the HONO Sources Constrained to Field Measurements at Rural North China Plain.

As nitrous acid (HONO) photolysis is an important source of hydroxyl radical (OH), apportionment of the ambient HONO sources is necessary to better understand atmospheric oxidation. Based on the data HONO-related species and various parameters measured during the one-month campaign at Wangdu (a rural site in North China plain) in summer 2014, a box model was adopted with input of current literature parametrizations for various HONO sources (nitrogen dioxide heterogeneous conversion, photoenhanced conversion, photolysis of adsorbed nitric acid and particulate nitrate, acid displacement, and soil emission) to reveal the relative importance of each source at the rural site. The simulation results reproduced the observed HONO production rates during noontime in general but with large uncertainty from both the production and destruction terms. NO2 photoenhanced conversion and photolysis of particulate nitrate were found to be the two major mechanisms with large potential of HONO formation but the associated uncertainty may reduce their importance to be nearly negligible. Soil nitrite was found to be an important HONO source during fertilization periods, accounted for (80 ± 6)% of simulation HONO during noontime. For some episodes of the biomass burning, only the NO2 heterogeneous conversion to HONO was promoted significantly. In summary, the study of the HONO budget is still far from closed, which would require a significant effort on both the accurate measurement of HONO and the determination of related kinetic parameters for its production pathways.

Exploring ozone pollution in Chengdu, southwestern China: A case study from radical chemistry to O3-VOC-NOx sensitivity.

We present the in-situ measurements in Chengdu, a major city in south west of China, in September 2016. The concentrations of ozone and its precursor were measured at four sites. Although the campaign was conducted in early autumn, up to 100 ppbv (parts per billion by volume) daily maximum ozone was often observed at all sites. The observed ozone concentrations showed good agreement at all sites, which implied that ozone pollution is a regional issue in Chengdu. To better understand the ozone formation in Chengdu, an observation based model is used in this study to calculate the ROx radical concentrations (ROx = OH + HO2 + RO2) and ozone production rate (P(O3)). The model predicts OH daily maximum is in the range of 4-8 × 106 molecules cm-3, and HO2 and RO2 are in the range of 3-6 × 108 molecules cm-3. The modelled radical concentrations show a distinct difference between ozone pollution and attainment period. The relative incremental reactivity (RIR) results demonstrate that anthropogenic VOCs reduction is the most efficient way to mitigate ozone pollution at all sites, of which alkenes dominate >50% of the ozone production. Empirical kinetic modelling approach shows that three out of four sites are under the VOC-limited regime, while Pengzhou is in a transition regime due to the local petrochemical industry. The ozone budget analysis showed that the local ozone production driven by the photochemical process is important to the accumulation of ozone concentrations.

Explicit diagnosis of the local ozone production rate and the ozone-NOx-VOC sensitivities.

In the troposphere, ozone is a harmful gas compound to both human health and vegetation. Ozone is produced from the reaction of NOx (NO + NO2) and VOCs (volatile organic compounds) with light. Due to the highly nonlinear relationships between ozone and its precursors, proper ozone mitigation relies on the knowledge of chemical mechanisms. In this study, an observation-based method is used to simulate ozone formation and elucidate its controlling factors for a rural site on the North China Plain. The instantaneous ozone production rate is calculated utilizing a box model using the dataset obtained from the Wangdu campaign. First, the model was operated in a time-dependent mode to calculate the ozone production rate at each time stamp. The calculated ozone formation rate showed a diurnal average maximum value of 17 ppbv/h (1-h diurnal averaged). The contribution of individual peroxy radicals to ozone production was analyzed. In addition, the functional dependence of calculated P(O3) reveals that ozone production was in a NOx-limited regime during the campaign. Furthermore, the missing peroxy radical source will further extend NOx-limited conditions to earlier in the day, making NOx limitation dominate more of a day than the current chemical model predicts. Finally, a multiple scenarios mode, also known as EKMA (empirical kinetic modeling approach), was used to simulate the response of P(O3) to the imaginary change in precursor concentrations. We found that ozone production was in the NOx-limited region. However, the use of NO2 measured by the molybdenum converter and/or the absence of a peroxy radical source in the current chemical model could over-emphasize the VOC-limited effect on ozone production.

In situ monitoring of atmospheric nitrous acid based on multi-pumping flow system and liquid waveguide capillary cell.

In the last four decades, various techniques including spectroscopic, wet chemical and mass spectrometric methods, have been developed and applied for the detection of ambient nitrous acid (HONO). We developed a HONO detection system based on long path photometry which consists of three independent modules i.e., sampling module, fluid propulsion module and detection module. In the propulsion module, solenoid pumps are applied. With solenoid pumps the pulsed flow can be computer controlled both in terms of pump stroke volume and pulse frequency, which enables the attainment of a very stable flow rate. In the detection module, a customized Liquid Waveguide Capillary Cell (LWCC) is used. The customized LWCC pre-sets the optical fiber in-coupling with the liquid wave guide, providing the option of fast startup and easy maintenance of the absorption photometry. In summer 2014, our system was deployed in a comprehensive campaign at a rural site in the North China Plain. More than one month of high quality HONO data spanning from the limit of detection to 5ppb were collected. Intercomparison of our system with another established system from Forschungszentrum Juelich is presented and discussed. In conclusion, our instrument achieved a detection limit of 10pptV within 2min and a measurement uncertainty of 7%, which is well suited for investigation of the HONO budget from urban to rural conditions in China.

[Transformation Mechanism and Sources of Secondary Inorganic Components in PM2.5 at an Agriculture Site (Quzhou) in the North China Plain in Summer].

Simultaneously on-line measurements of major water-soluble inorganic ions and gaseous pollutants were performed from June 9 to July 11, 2014 at Quzhou, an agriculture site in the North China Plain using a gas-aerosol collector (GAC) and ion chromatograph (IC), aiming to track the diurnal variation rule of secondary inorganic components and gas-phase precursors as well as their interactions. The transformation mechanism and sources of fine particles (PM2.5) were also discussed. The results showed that these water-soluble ions in PM2.5 and their gas-phase precursors varied regularly. As the dominant ionic components of PM2.5 (accounting for 76.23%), the average concentrations of SO4(2-), NH4(+), NO3(-) were 26.28 µg x m(-3), 18.08 µg x m(-3) and 16.36 µg m(-3) respectively. Among the precursor gases, the NH3, generated from the discharges of local agricultural activities, displayed a significantly higher concentration at an average value of 44.85 µg x m(-3). The average fine sulfate and nitrate oxidation ratios (SOR and NOR) were SOR = 0.60, NOR = 0.30, revealing the remarkable characteristics of secondary pollution. As could be found from the relevant analysis, the NH4(+) of Quzhou showed well relations with NO3(-) and SO4(2-), and the environment here was rich of ammonia. The NH4(+) existed in the form of (NH4)2SO4 and the generation of NO3(-) was limited by the HNO3. From the analysis for the equilibrium of NH4NO3, we observed that the atmospheric environment of Quzhou was adverse to the generation and maintenance of NH4NO3 during the daytime,in contrast with the night. Integrated with the study, the results displayed that the secondary transformation was the main source of fine particles in Quzhou, and the NH3 from field and compost was the significant factor leading to the high value of S-N-A.

[Improvement and application of the method for determination of OCEC split].

Aerosol samples were collected in Beijing (BD) and Atlanta (GT) from July to August in 2011 using a Micro-Orifice Uniform Deposit Impactor (MOUDI) (0.18-18 microm, eight-stage) for organic carbon (OC) and elemental carbon (EC) measurement (Sunset Laboratory Inc, USA). The laser intensity of blank filters decreased with temperature in the process of OC & EC analysis because the structure of quartz filters was changed when burned which largely affected the determination of low concentration samples' splits. It would increase the accuracy of OC & EC split to determine it manually after the change of blank filter's laser intensity was recouped. The concentrations and size distributions of OC & EC using the improved method were different from taking the moment when oxygen was introduced as the split. The split may appear before oxygen addition, when the sample was rich in metal or substances that can be decomposed after heated. The concentrations of carbonaceous components were higher at BD than those at GT. The size distributions of OC showed a bimodal pattern with peaks appeared in the particles with size of (0.56-1.0) microm and (3.2-5.6) microm. The peak concentrations of OC were (2.82 +/- 1.59) microg x m(-3) and (1.95 +/- 0.76) microg x m(-3) at BD, and (1.28 +/- 0.41) microg x m(-3) and (0.64 +/- 0.19) microg x m(-3) at GT. EC showed a bimodal pattern at BD with peaks in particles with size of (0.56-1.0) microm and (3.2-5.6) microm, while showed a trimodal pattern at GT. The peak concentrations at BD were (0.32 +/- 0.24) microg x m(-3) and (0.26 +/- 0.19) microg x m(-3). EC at GT was preferably enriched in particles with size of (0.18-0.56) microm, the mass concentrations of EC in this size accounted for 44.6%. The OC and EC were more concentrated in accumulation mode at GT than those at BD, the reason may be that the main pollution source of GT is motor vehicle emission, while there are more industrial gas emissions at BD.