Nitrate Aerosol Research Articles

Evaluating the Importance of Nitrate‐Containing Aerosols for the Asian Tropopause Aerosol Layer

AbstractThe Asian Summer Monsoon (ASM) convection transports aerosols and their precursors from the boundary layer to the upper troposphere and lower stratosphere (UTLS). This process forms an annually recurring aerosol layer near the tropopause. Recent observations have revealed a distinct property of the aerosol layer over the ASM region, it is nitrate‐rich. We present a newly implemented aerosol formation algorithm that enhances the representation of nitrate aerosol in the Community Aerosol and Radiation Model for Atmospheres (CARMA) coupled with the Community Earth System Model (CESM). The simulated aerosol chemical composition, as well as vertical distributions of aerosol size and mass, are evaluated using in situ and remote sensing observations. The simulated concentrations (ammonium, nitrate, and sulfate) and size distributions are generally within the error bars of data. We find nitrate, organics, and sulfate contribute significantly to the UTLS aerosol concentration between 15°–45°N and 0°–160°E. The two key formation mechanisms of nitrate‐containing aerosols in the ATAL are ammonium neutralization to form ammonium nitrate in regions where convection is active, and condensation of nitric acid in regions of cold temperature. Furthermore, including nitrate formation in the model doubles the surface area density in the tropical tropopause region between 15°–45°N and 0°–160°E, which alters the chlorine partitioning and subsequently impacts the rate of ozone depletion.

Multiphase Reactions of Hydrocarbons Into an Air Quality Model With CAMx‐UNIPAR: Impacts of Humidity and NOx on Secondary Organic Aerosol Formation in the Southern USA

AbstractSecondary organic aerosol (SOA) mass in the Southern USA during winter‐spring 2022 was simulated by integrating Comprehensive Air quality Model with extensions (CAMx) with the UNIfied Partitioning‐Aerosol phase Reaction (UNIPAR) model, which predicts SOA formation via multiphase reactions of hydrocarbons. UNIPAR streamlines multiphase partitioning of oxygenated products and their heterogeneous reactions by using explicitly predicted products originating from 10 aromatics, 3 biogenics, and linear/branched alkanes (C9‐C24). UNIPAR simulations were compared with those using Secondary Organic Aerosol Partitioning (SOAP) model, which uses simple surrogate products for each precursor. Both UNIPAR and SOAP showed similar tendencies in SOA mass but slightly underpredicted against observations at given five ground sites. However, SOA compositions and their sensitivity to environmental variables (sunlight, humidity, NOx, and SO2) were different between two models. In CAMx‐UNIPAR, SOA originated predominantly from alkanes, terpenes, and isoprene, and was influenced by humidity, showing high SOA concentrations with wet‐inorganic salts, which accelerated aqueous reactions of reactive organic products. NO2 was positively correlated with biogenic SOA because elevated levels of nitrate radicals and hygroscopic nitrate aerosol effectively oxidized biogenic hydrocarbons at night and promoted SOA growth via organic heterogeneous chemistry, respectively. Anthropogenic SOA, which formed mainly via daytime oxidation with OH radicals, was weakly and negatively correlated with NO2 in cities. In CAMx‐UNIPAR, the sensitivity of SOA to aerosol acidity (neutral vs. acidic aerosol at cation/anion = 0.62) was dominated by isoprene SOA. The reduction of NOx emissions could effectively mitigate SOA burdens in the Southern USA where biogenic hydrocarbons are abundant.

Aerosol composition, air quality, and boundary layer dynamics in the urban background of Stuttgart in winter

Abstract. Aerosol distributions are of great relevance for air quality, especially for cities like Stuttgart, which has limited air exchange due to its location in a basin. We collected a comprehensive set of data from remote sensing and in situ methods including radiosondes for the urban background of downtown Stuttgart to determine the impact of boundary layer mixing processes on local air quality and to evaluate the simulation results of the high-resolution large eddy simulation (LES) model PALM-4U at 10 m grid spacing. Stagnant meteorological conditions caused accumulation of aerosols, and chemical composition analysis shows that ammonium nitrate (37 ± 9 %) and organic aerosol (OA; 34 ± 9 %) dominated during this winter study. Case studies show that clouds during previous nights can weaken temperature inversion and accelerate boundary layer mixing after sunrise by up to 3 h. This is important for ground-level aerosol dilution during the morning rush hour. Furthermore, our observations validate results of the LES model PALM-4U in terms of boundary layer heights and aerosol mixing for 48 h. The simulated aerosol concentrations follow the trend of our observations but are still underestimated by a factor of 4.5 ± 2.1 due to missing secondary aerosol formation processes and uncertainties of emissions and boundary conditions in the model. This paper firstly evaluates the PALM-4U model performance in simulating aerosol spatio-temporal distributions, which can help to improve the LES model and to better understand sources and sinks for air pollution as well as the role of horizontal and vertical transport.

Effects of Ammonia Mitigation on Secondary Organic Aerosol and Ammonium Nitrate Particle Formation in Photochemical Reacted Gasoline Vehicle Exhausts

Gaseous air pollutants emitted primarily by anthropogenic sources form secondary products through photochemical reactions, complicating the regulatory analysis of anthropogenic emissions in the atmosphere. We used an environmental chassis dynamometer and a photochemical smog chamber to conduct a parameter sensitivity experiment to investigate the formation of secondary products from a gasoline passenger car. To simulate the mitigation of ammonia emissions from gasoline vehicle exhausts assuming future emission controls and to allow photochemical oxidation and aging of the vehicle exhaust, ammonia was selectively removed by a series of five denuders installed between the vehicle and photochemical smog chamber. Overall, there were no differences in the formation of secondary organic aerosols and ozone with or without ammonia mitigation. However, the potential for ammonium nitrate particle formation was significantly reduced with ammonia mitigation. In addition, ammonia mitigation resulted in increased aerosol acidity due to nitric acid in the gas phase not being neutralized by ammonia and condensing onto the liquid particle phase, indicating a potentially important secondary effect associated with ammonia mitigation. Thus, we provide new insights into the effects of ammonia mitigation on secondary emissions from gasoline vehicle exhaust and into a potentially useful experimental approach for determining primary and secondary emissions.

Dual isotope analysis reveals the COVID-19 lockdown impact on nitrate aerosol sources and formation pathways in Shanghai

Nitrate (NO3−) is an important contributor to PM2.5 which can adversely affect the environment and human health. A noticeable decrease in NOx concentrations has been reported due to the lockdown measures implemented to curb the spread of Corona Virus Disease 2019 (COVID-19). However, questions remain, regarding the nonlinear relationship between NOx and NO3−. Here, we collected PM2.5 samples in two periods, before and during the lockdown of COVID-19 in Shanghai. Dual isotopes (δ18O-NO3− and δ15N-NO3−) of NO3− were measured to investigate the formation pathways and potential sources of NO3−. The results showed that the concentration of NO3− decreased significantly during the lockdown period compared to the period before the lockdown. Additionally, the hydroxyl pathway was the dominant contributor to NO3− production during the lockdown period, while N2O5 hydrolyses dominated the formation of NO3− before the lockdown. This change is largely attributable to alterations in the oxidative potential of the environment. In comparison to the period preceding the lockdown, the relative contributions of each NOx source remained largely unchanged throughout the lockdown periods. Nevertheless, the concentration of NO3− contributed by each NOx source exhibited a notable decline, particularly the mobile sources and coal combustion. Furthermore, the reduction extent of NO3− due to the lockdown period was also greater than the reduction during the Clean Air Actions (2013–2017). Our findings provide evidence that the COVID-19 lockdown led to a decrease in NO3− concentration due to changes in the formation pathway and reductions in NOx emissions from various sources.

Impact of Heatwaves and Declining NOx on Nocturnal Monoterpene Oxidation in the Urban Southeastern United States.

Nighttime oxidation of monoterpenes (MT) via the nitrate radical (NO3) and ozone (O3) contributes to the formation of secondary organic aerosol (SOA). This study uses observations in Atlanta, Georgia from 2011-2022 to quantify trends in nighttime production of NO3 (PNO3) and O3 concentrations and compare to model outputs from the EPA's Air QUAlity TimE Series Project (EQUATES). We present urban-suburban gradients in nighttime NO3 and O3 concentrations and quantify their fractional importance (F) for MT oxidation. Both observations and EQUATES show a decline in PNO3, with modeled PNO3 declining faster than observations. Despite decreasing PNO3, we find that NO3 continues to dominate nocturnal boundary layer (NBL) MT oxidation (FNO3 = 60%) in 2017, 2021, and 2022, which is consistent with EQUATES (FNO3 = 80%) from 2013-2019. This contrasts an anticipated decline in FNO3 based on prior observations in the nighttime residual layer, where O3 is the dominant oxidant. Using two case studies of heatwaves in summer 2022, we show that extreme heat events can increase NO3 concentrations and FNO3, leading to short MT lifetimes (<1 h) and high gas-phase organic nitrate production. Regardless of the presence of heatwaves, our findings suggest sustained organic nitrate aerosol formation in the urban SE US under declining NOx emissions, and highlight the need for improved representation of extreme heat events in chemistry-transport models and additional observations along urban to rural gradients.

A Novel Apportionment Method Utilizing Particle Mass Size Distribution across Multiple Particle Size Ranges

Many cities in China are facing the dual challenge of PM2.5 and PM10 pollution. There is an urgent need to develop a cost-effective method that can apportion both with high-time resolution. A novel and practical apportionment method is presented in this study. It combines the measurement of particle mass size distribution (PMSD) with an optical particle counter (OPC) and the algorithm of normalized non-negative matrix factorization (N-NMF). Applied in the city center of Baoding, Hebei, this method separates four distinct pollution factors. Their sizes (ordered from the smallest to largest) range from 0.16 μm to 0.6 μm, 0.16 μm to 1.0 μm, 0.5 μm to 17.0 μm, and 2.0 μm to 20.0 μm, respectively. They correspondingly contribute to PM2.5 (PM10) with portions of 26% (17%), 37% (26%), 33% (41%), and 4% (16%), respectively, on average. The smaller three factors are identified as combustion, secondary, and industrial aerosols because of their high correlation with carbonaceous aerosols, nitrate aerosols, and trace elements of Fe/Mn/Ca in PM2.5, respectively. The largest-sized factor is linked to dust aerosols. The primary origin regions, oxidation degrees, and formation mechanisms of each source are further discussed. This provides a scientific basis for the comprehensive management of PM2.5 and PM10 pollution.

Important contributions of natural gas combustion to atmospheric nitrate aerosols in China: Insights from stable nitrogen isotopes

Important contributions of natural gas combustion to atmospheric nitrate aerosols in China: Insights from stable nitrogen isotopes

Assessing the nonlinearity of wintertime PM2.5 formation in response to precursor emission changes in North China with the adjoint method

Abstract While China’s clean air actions implemented since 2013 have been effective in mitigating PM2.5 air pollution, the large emission reductions during the COVID-19 lockdown period in early 2020 did not similarly alleviate PM2.5 pollution in North China, reflecting a distinct nonlinear chemical response of PM2.5 formation to emission changes. Here we apply emission-concentration relationships for PM2.5 diagnosed using the adjoint approach to quantitatively assess how chemical nonlinearity affects PM2.5 over Beijing in February 2020 in response to two emission reduction scenarios: the COVID-19 lockdown and 2013–2017 emission controls. We find that, in the absence of chemical nonlinearity, the COVID-19 lockdown would decrease PM2.5 in Beijing by 17.9 μg m–3, and the 2013–2017 emission controls resulted in a larger decrease of 54.2 μg m–3 because of greater reductions of SO2 and primary aerosol emissions. Chemical nonlinearity offset the decrease for Beijing PM2.5 by 3.4 μg m–3 during the lockdown due to enhanced sensitivity of aerosol nitrate to NO x emissions, but enhanced the efficiency of 2013–2017 emission controls by 11.9 μg m–3 due to the weakened heterogeneous reaction of sulfate. Such nonlinear chemical effects are important to estimate and consider when designing or assessing air pollution control strategies.

Diverging trends in aerosol sulfate and nitrate measured in the remote North Atlantic in Barbados are attributed to clean air policies, African smoke, and anthropogenic emissions.

Sulfate and nitrate aerosols degrade air quality, modulate radiative forcing and the hydrological cycle, and affect biogeochemical cycles, yet their global cycles are poorly understood. Here, we examined trends in 21 years of aerosol measurements made at Ragged Point, Barbados, the easternmost promontory on the island located in the eastern Caribbean Basin. Though the site has historically been used to characterize African dust transport, here we focused on changes in nitrate and non-sea-salt (nss) sulfate aerosols from 1990-2011. Nitrate aerosol concentrations averaged over the entire period were stable at 0.59 μg m-3 ± 0.04 μg m-3, except for elevated nitrate concentrations in the spring of 2010 and during the summer and fall of 2008 due to the transport of biomass burning emissions from both northern and southern Africa to our site. In contrast, from 1990 to 2000, nss-sulfate decreased 30% at a rate of 0.023 μg m-3 yr-1, a trend which we attribute to air quality policies enacted in the United States (US) and Europe. From 2000-2011, sulfate gradually increased at a rate of 0.021 μg m-3 yr-1 to pre-1990s levels of 0.90 μg m-3. We used the Community Multiscale Air Quality (CMAQ) model simulations from the EPA's Air QUAlity TimE Series (EQUATES) to better understand the changes in nss-sulfate after 2000. The model simulations estimate that increases in anthropogenic emissions from Africa explain the increase in nss-sulfate observed in Barbados. Our results highlight the need to better constrain emissions from developing countries and to assess their impact on aerosol burdens in remote source regions.

Hemispherical scale mechanisms of nitrate formation in global marine aerosols

Nitrogen oxides (NOx) in the atmosphere directly affect air quality; however, their oxidation products (e.g., nitrate) are essential nutrients in terrestrial and marine ecosystems. To date, the mechanism and rate of nitrate formation in the global-scale marine boundary layer remains uncertain. Herein, aerosol nitrate isotopes covering the global ocean were analysed and observations indicated that nitrate formation was dominated by the proportion between the hydroxyl radical (daytime) and ozone (nighttime) pathways in the Northern Hemisphere (NH), whereas it changed to the BrO (Antarctic iceberg emission) pathway in the Southern Hemisphere (SH). These differences in the pathways suggested that the NOx removal (nitrate formation) efficiency was higher in the NH, which could be responsible for the much higher nitrate concentrations in the NH than in the SH (over twice). This study can assist in formulating effective policies to mitigate global NOx pollution and improve our understanding of the impact of increasing NOx concentrations on global ocean productivity.

Investigating the convective transport possibilities of lower-atmospheric pollutants to the UTLS region using rainwater and aerosol chemical characterization

Various attempts using different platforms to understand the chemical composition of the Asian Tropopause Aerosol Layer (ATAL) have concluded that it primarily consists of nitrate (NO3−) aerosols. Recent in-situ measurements from aircraft flying through ATAL have suggested that ammonia (NH3) pollution from Asia could serve as the precursor for nitrate aerosols in ATAL through gas-to-particle formation after undergoing convective uplift to the Upper Troposphere and Lower Stratosphere (UTLS) regions. In this study, we aimed to investigate the potential pathways of convective transport of lower-atmospheric pollutants by analysing the chemical composition of rainwater and aerosols in a highly convective region, Kolkata (Head Bay of Bengal), India. We utilized the PILS-IC system established at Kolkata Camp Observatory of the National Atmospheric Research Laboratory (KCON). The analysis revealed a significant dominance of NH4+ and NO3− ions in both rainwater and aerosol samples during the monsoon and post-monsoon seasons, with the dominance increasing during the post-monsoon season. Air mass trajectories indicated a clear influence of the Indo-Gangetic Plain (IGP) region during the post-monsoon season, which is well-known for its dense agricultural activities and industries. High concentrations of NH3 even at higher altitudes, have been observed in Atmospheric Infrared Sounder (AIRS) measurements. Moreover, using Outgoing Longwave Radiation (OLR) and vertical wind as proxies for tropical deep convection and updrafts/downdrafts, respectively, we found evidence supporting the possibility of convective transport of these lower-atmospheric pollutants to the UTLS regions during the monsoon season. In conclusion, this study provides evidence for the potential convective transport of lower-atmospheric pollutants, including NH3 and other precursor gases, to higher levels. These pollutants could partially serve as the source of nitrate aerosols in the ATAL through gas-to-particle formation processes.

Evaluation of a new real-time source apportionment system of PM2.5 and its implication on rapid aging of vehicle exhaust

Accurate identification and rapid analysis of PM2.5 sources and formation mechanisms are essential to mitigate PM2.5 pollution. However, studies were limited in developing a method to apportion sources to the total PM2.5 mass in real-time. In this study, we developed a real-time source apportionment method based on chemical mass balance (CMB) modeling and a mass-closure PM2.5 composition online monitoring system in Shenzhen, China. Results showed that secondary sulfate, secondary organic aerosol (SOA), vehicle emissions and secondary nitrate were the four major PM2.5 sources during autumn 2019 in Shenzhen, together contributed 76 % of PM2.5 mass. The novel method was verified by comparing with other source apportionment methods, including offline filter analysis, aerosol mass spectrometry, and carbon isotopic analysis. The comparison of these methods showed that the new real-time method obtained results generally consistent with the others, and the differences were interpretable and implicative. SOA and vehicle emissions were the major PM2.5 and OA contributors by all methods. Further investigation on the OA sources indicated that vehicle emissions were not only the main source of primary organic aerosol (POA), but also the main contributor to SOA by rapid aging of the exhaust in the atmosphere. Our results demonstrated the great potential of the new real-time source apportionment method for aerosol pollution control and deep understandings on emission sources.

Dual isotopic evidence of δ15N and δ18O for priority control of vehicle emissions in a megacity of East China: Insight from measurements in summer and winter

The source apportionment and main formation pathway of nitrate aerosols in China are not yet fully understood. In this study, PM2.5 samples were collected in Shanghai in the summer and winter of 2019. Water-soluble inorganic ions and isotopic signatures of stable nitrogen (δ15N-NO3−) and stable oxygen (δ18O-NO3−) in PM2.5 were determined. The results showed that NO3− was less important in summer (NO3−/SO42− = 0.4 ± 0.8), while it became the dominant species in winter (52.1 %). The average values of δ15N-NO3− and δ18O-NO3− in summer were + 2.0 ± 6.1 ‰ and 63.3 ± 9.4 ‰ respectively, which were significantly lower than those in winter (+7.2 ± 3.4 ‰ and 88.3 ± 12.1 ‰), indicating discrepancies between NOx sources and nitrate formation pathways. Both δ15N-NO3− and δ18O-NO3− were elevated at night, demonstrating that N2O5 hydrolysis contributed to the nocturnal nitrate increase even in summer. The contribution of the OH oxidation pathway to nitrate aerosols averaged at 70.5 ± 17.0 % in summer and N2O5 hydrolysis dominated the nitrate production in winter (approximately 80 %). On average, vehicle exhaust, coal combustion, natural gas burning, and soil emission contributed 50.7 %, 21.5 %, 15.9 %, and 11.9 %, respectively, to nitrate aerosols in summer, and contributed 56.8 %, 23.9 %, 13.6 %, and 5.7 %, respectively, to nitrate production in winter. Notably, natural gas burning is a non-negligible source of nitrate aerosols in Shanghai. In contrast to an inverse correlation between δ15N-NO3− and PM2.5, the value of δ18O-NO3− was positively correlated with nitrate concentration and aerosol liquid water content (ALWC) in winter, suggesting that explosive growth of nitrate was driven by continuous accumulation of N-depleted NOx and rapid N2O5 hydrolysis under calm and humid conditions. To continuously improve air quality, priority control should be given to vehicle emissions as the dominant source of NOx and volatile organic compounds (VOCs) in Shanghai.

Insights into anthropogenic impact on atmospheric inorganic aerosols in the largest city of the Tibetan Plateau through multidimensional isotope analysis

Particulate inorganic nitrogen aerosols (PIN) significantly influence air pollution and pose health risks worldwide. Despite extensive observations on ammonium (pNH4+) and nitrate (pNO3−) aerosols in various regions, their key sources and mechanisms in the Tibetan Plateau remain poorly understood. To bridge this gap, this study conducted a sampling campaign in Lhasa, the Tibetan Plateau's largest city, with a focus on analyzing the multiple isotopic signatures (δ15N, ∆17O). These isotopes were integrated into a Bayesian mixing model to quantify the source contributions and oxidation pathways for pNH4+ and pNO3−. Our results showed that traffic was the largest contributor to pNH4+ (31.8 %), followed by livestock (25.4 %), waste (21.8 %), and fertilizer (21.0 %), underscoring the impact of vehicular emissions on urban NH3 levels in Lhasa. For pNO3−, coal combustion emerged as the largest contributor (27.3 %), succeeded by biomass burning (26.3 %), traffic emission (25.3 %), and soil emission (21.1 %). In addition, the ∆17O-based model indicated a dominant role of NO2 + OH (52.9 %) in pNO3− production in Lhasa, which was similar to previous observations. However, it should be noted that the NO3 + volatile organic component (VOC) contributed up to 18.5 % to pNO3− production, which was four times higher than the Tibetan Plateau's background regions. Taken together, the multidimensional isotope analysis performed in this study elucidates the pronounced influence of anthropogenic activities on PIN in the atmospheric environment of Lhasa.

Impact of soil–atmosphere HONO exchange on concentrations of HONO and O3 in the North China Plain

Nitrous acid (HONO) is an important precursor of the hydroxyl radical (OH) and plays a vital role in atmospheric photochemistry and nitrogen cycling. Soil emissions have been considered as a potential source of HONO. Lately, the HONO emission via soil-atmosphere exchange (ESA-exchange) from soil nitrite has been validated and quantified through chamber experiments, but has not been assessed in the real atmosphere. We coupled ESA-exchange and the other seven potential sources of HONO (i.e., traffic, indoor and soil bacterial emissions, heterogeneous reactions on ground and aerosol surfaces, nitrate photolysis, and acid displacement) into the Weather Research and Forecasting model with Chemistry (WRF-Chem), and found that diurnal variations of the soil emission flux at the Wangdu site were well simulated. During the non-fertilization period, ESA-exchange contributed ∼28 % and ∼35 % of nighttime and daytime HONO, respectively, and enhanced the net ozone (O3) production rate by ∼8 % across the North China Plain (NCP). During the preintensive/intensive fertilization period, the maximum ESA-Exchange contributions attained ∼70 %/83 % of simulated HONO in the afternoon across the NCP, definitely asserting its dominance in HONO production. ESA-Exchange enhanced the OH production rate via HONO photolysis by ∼3.5/7.0 times, and exhibited an increase rate of ∼13 %/20 % in the net O3 production rate across the NCP. The total enhanced O3 due to the eight potential HONO sources ranged from ∼2 to 20 ppb, and ESA-exchange produced O3 enhancements of ∼1 to 6 ppb over the three periods. Remarkably, the average contribution of ESA-exchange to the total O3 enhancements remained ∼30 %. This study suggests that ESA-exchange should be included in three-dimensional chemical transport models and more field measurements of soil HONO emission fluxes and soil nitrite levels are urgently required.

Continental Emissions Influence the Sources and Formation Mechanisms of Marine Nitrate Aerosols in Spring Over the Bohai Sea and Yellow Sea Inferred From Stable Isotopes

AbstractThe influence of continental emissions on the origin and formation mechanisms of atmospheric particulate nitrate (ρ‐NO3−) aerosols in the marine boundary layer remains unclear. Here, synchronous observations of nitrogen isotope ratios (δ15N–NO3−) and oxygen isotope anomaly (Δ17O–NO3−) in ρ‐NO3− were conducted across the Yellow Sea and Bohai Sea in Eastern China. Nitrate concentrations, δ15N–NO3− and Δ17O–NO3− exhibited a pronounced north‐to‐south latitudinal gradient. Combined with backward air mass trajectory analysis, the high nitrate concentration and isotopic characteristics in the northern sea area were found to be affected by the continental outflow near China while the low values in the southern sea area were more related to the oceanic inflow. Stable isotope analysis in R (SIAR) indicated that near the northern sea area, the nitrate radicals (NO3) reacted with hydrocarbons (HC) or dimethyl sulfides (DMS) pathway (NO3 + HC/DMS) played a leading role in nitrate production, whereas the NO2 + OH pathway dominated near the southern sea area. Nitrate in the northern seas originated mainly from nitrogen oxides (NOx = NO + NO2, the gaseous precursor of nitrate) emitted from continental sources, especially coal combustion and biomass burning. While closer to the southern seas, the proportion of NOx generated in the marine environment (from ship and biogenic emissions) increased. Overall, the differential relative contributions of continental and marine atmospheric chemistry and NOx sources lead to the spatial distribution characteristics of atmospheric nitrate concentrations and isotopic values over the Yellow and Bohai Seas.

Quantification of NOx sources contribution to ambient nitrate aerosol, uncertainty analysis and sensitivity analysis in a megacity

Dual isotopes of nitrogen and oxygen of NO3− are crucial tools for quantifying the formation pathways and precursor NOx sources contributing to atmospheric nitrate. However, further research is needed to reduce the uncertainty associated with NOx proportional contributions. The acquisition of nitrogen isotopic composition from NOx emission sources lacks regulation, and its impact on the accuracy of contribution results remains unexplored. This study identifies key influencing factors of source isotopic composition through statistical methods, based on a detailed summary of δ15N-NOx values from various sources. NOx emission sources are classified considering these factors, and representative means, standard deviations, and 95 % confidence intervals are determined using the bootstrap method. During the sampling period in Tianjin in 2022, the proportional nitrate formation pathways varied between sites. For suburban and coastal sites, the ranking was fP1(NO2 + OH radical) >fP2(N2O5 + H2O) >fP3(NO3 + DMS/HC), while the rural site exhibited similar fractional contributions from all three formation pathways. Fossil fuel NOx sources consistently contributed more than non-fossil NOx sources in each season among three sites. The uncertainties in proportional contributions varied among different sources, with coal combustion and biogenic soil emission showing lower uncertainties, suggesting more stable proportional contributions than other sources. The sensitivity analysis clearly identifies that the isotopic composition of 15N-enriched and 15N-reduced sources significantly influences source contribution results, emphasizing the importance of accurately characterizing the localized and time-efficient nitrogen isotopic composition of NOx emission sources. In conclusion, this research sheds light on the importance of addressing uncertainties in NOx proportional contributions and emphasizes the need for further exploration of nitrogen isotopic composition from NOx emission sources for accurate atmospheric nitrate studies.

Air Quality and Health Impacts of Onshore Oil and Gas Flaring and Venting Activities Estimated Using Refined Satellite-Based Emissions.

Emissions from flaring and venting (FV) in oil and gas (O&G) production are difficult to quantify due to their intermittent activities and lack of adequate monitoring and reporting. Given their potentially significant contribution to total emissions from the O&G sector in the United States, we estimate emissions from FV using Visible Infrared Imaging Radiometer Suite satellite observations and state/local reported data on flared gas volume. These refined estimates are higher than those reported in the National Emission Inventory: by up to 15 times for fine particulate matter (PM2.5), two times for sulfur dioxides, and 22% higher for nitrogen oxides (NOx). Annual average contributions of FV to ozone (O3), NO2, and PM2.5 in the conterminous U.S. (CONUS) are less than 0.15%, but significant contributions of up to 60% are found in O&G fields with FV. FV contributions are higher in winter than in summer months for O3 and PM2.5; an inverse behavior is found for NO2. Nitrate aerosol contributions to PM2.5 are highest in the Denver basin whereas in the Permian and Bakken basins, sulfate and elemental carbon aerosols are the major contributors. Over four simulated months in 2016 for the entire CONUS, FV contributes 210 additional instances of exceedances to the daily maximum 8-hr average O3 and has negligible contributions to exceedance of NO2 and PM2.5, given the current form of the national ambient air quality standards. FV emissions are found to cause over $7.4 billion in health damages, 710 premature deaths, and 73,000 asthma exacerbations among children annually.

Particle phase state and aerosol liquid water greatly impact secondary aerosol formation: insights into phase transition and its role in haze events

Abstract. The particle phase state is crucial for reactive gas uptake, heterogeneous, and multiphase chemical reactions, thereby impacting secondary aerosol formation. This study provides valuable insights into the significance of particle-phase transition and aerosol liquid water (ALW) in particle mass growth during winter. Our findings reveal that particles predominantly exist in a semi-solid or solid state during clean winter days with ambient relative humidity (RH) below 30 %. However, a non-liquid to liquid phase transition occurs when the ALW mass fraction exceeds 15 % (dry mass) at transition RH thresholds of 40 %–60 %. During haze episodes, the transformation rates of sulfate and nitrate aerosols rapidly increase through phase transition and increased ALW by 48 % and 11 %, respectively, resulting in noticeable increases in secondary inorganic aerosols (SIA). The presence of abundant ALW, favored by elevated RH and higher proportion of SIA, facilitates the partitioning of water-soluble compounds from the gas to the particle phase, as well as heterogeneous and aqueous processes in liquid particles. This leads to a substantial increase in the formation of secondary organic aerosols and elevated aerosol oxidation. Consequently, the overall hygroscopicity parameters exhibit a substantial enhancement, with a mean value of 23 %. These results highlight phase transition as a key factor initiating the positive feedback loops between ALW and secondary aerosol formation during haze episodes over the North China Plain. Accurate predictions of secondary aerosol formation necessitate explicit consideration of the particle phase state in chemical transport models.