Alder expansion stimulates nitrogen oxide (NOx) emissions from southern Eurasian permafrost peatlands.

Nitrogen oxides (NOx) play an important role for atmospheric chemistry and radiative forcing. However, NOx emissions from the vast northern circumpolar permafrost regions have not been studied in situ due to limitations of measurement techniques. Our goals were to validate the offline analytical technique, and based on this, to widely quantify in situ NOx emissions from peatlands in the southern Eurasian permafrost region. To this end, we conducted a comparison of online and offline flux measurements in 2018 and 2019 using the synthetic air flushing, steady-state opaque chamber method. With differences in annual average and cumulative fluxes less than 0.1 µg N m-2 h-1 and 0.01 kg N ha-1 year-1, the online and offline fluxes were in good agreement, demonstrating the feasibility of conducting offline measurements in remote regions without power supply. The flux measurements over 2 years showed obvious NOx emissions of 0.05-0.14 and 0.13-0.30 kg N ha-1 year-1 in the hollow and hummock microtopography of permafrost peatlands, respectively. The rapid expansion of alder (Alnus sibirica) in the peatlands induced by permafrost degradation significantly increased soil mineral N contents and NOx emissions depending on the age of alder (0.64-1.74 and 1.44-2.20 kg N ha-1 year-1 from the alder forests with tree ages of 1-10 years and 11-20 years, respectively). Alder expansion also intensively altered the thermal state of permafrost including the sharp increases of soil temperatures during the non-growing season from October to April and active layer thickness. This study provides the first in situ evidences of NOx emissions from the northern circumpolar permafrost regions and uncovers the well-documented expansion of alders can substantially stimulate NOx emissions and thus, significantly affect air quality, radiative forcing, and ecosystem productivity in the pristine regions.

Large Seasonal Variation in Nitrogen Isotopic Abundances of Ammonia Volatilized from a Cropland Ecosystem and Implications for Regional NH3 Source Partitioning.

Ammonia (NH3) volatilization from agricultural lands is a main source of atmospheric reduced nitrogen species (NHx). Accurately quantifying its contribution to regional atmospheric NHx deposition is critical for controlling regional air nitrogen pollution. The stable nitrogen isotope composition (expressed by δ15N) is a promising indicator to trace atmospheric NHx sources, presupposing a reliable nitrogen isotopic signature of NH3 emission sources. To obtain more specific seasonal δ15N values of soil NH3 volatilization for reliable regional seasonal NH3 source partitioning, we utilized an active dynamic sampling technique to measure the δ15N-NH3 values volatilized from maize cropping land in northeast China. These values varied from -38.0 to -0.2‰, with a significantly lower rate-weighted value observed in the early period (May-June, -30.5 ± 6.7‰) as compared with the late period (July-October, -8.5 ± 4.3‰). Seasonal δ15N-NH3 variations were related to the main NH3 production pathway, degree of soil ammonium consumption, and soil environment. Bayesian isotope mixing model analysis revealed that without considering the seasonal δ15N variation in soil-volatilized NH3 could result in an overestimate by up to absolute 38% for agricultural volatile NH3 to regional atmospheric bulk ammonium deposition during July-October, further demonstrating that it is essential to distinguish seasonal δ15N profile of agricultural volatile NH3 in regional source apportionment.

Apportioning Atmospheric Ammonia Sources across Spatial and Seasonal Scales by Their Isotopic Fingerprint.

Mitigating ammonia (NH3) emissions is a significant challenge, given its well-recognized role in the troposphere, contributing to secondary particle formation and impacting acid rain. The difficulty arises from the highly uncertain attribution of atmospheric NH3 to specific emission sources, especially when accounting for diverse environments and varying spatial and temporal scales. In this study, we established a refined δ15N fingerprint for eight emission sources, including three previously overlooked sources of potential importance. We applied this approach in a year-long case study conducted in urban and rural sites located only 40 km apart in the Shandong Peninsula, North China Plain. Our findings highlight that although atmospheric NH3 concentrations and seasonal trends exhibited similarities, their isotopic compositions revealed significant distinctions in the primary NH3 sources. In rural areas, although agriculture emerged as the dominant emission source (64.2 ± 19.5%), a previously underestimated household stove source also played a considerably greater role, particularly during cold seasons (36.5 ± 12.5%). In urban areas, industry and traffic (33.5 ± 15.6%) and, surprisingly, sewage treatment (27.7 ± 11.3%) associated with high population density were identified as the major contributors. Given the relatively short lifetime of atmospheric NH3, our findings highlight the significance of the isotope approach in offering a more comprehensive understanding of localized and seasonal influences of NH3 sources compared to emissions inventories. The refined isotopic fingerprint proves to be an effective tool in distinguishing source contributions across spatial and seasonal scales, thereby providing valuable insights for the development of emission mitigation policies aimed at addressing the increasing NH3 burden on the local atmosphere.

Summertime Urban Ammonia Emissions May Be Substantially Underestimated in Beijing, China.

Ammonia (NH3) is critical to the nitrogen cycle and PM2.5 formation, yet a great deal of uncertainty exists in its urban emission quantifications. Model-underestimated NH3 concentrations have been reported for cities, yet few studies have provided an explanation. Here, we explore reasons for severe WRF-Chem model underestimations of NH3 concentrations in Beijing in August 2018, including simulated gas-particle partitioning, meteorology, regional transport, and emissions, using spatially refined (3 km resolution) NH3 emission estimates in the agricultural sector for Beijing-Tianjin-Hebei and in the traffic sector for Beijing. We find that simulated NH3 concentrations are significantly lower than ground-based and satellite observations during August in Beijing, while wintertime underestimations are much more moderate. Further analyses and sensitivity experiments show that such discrepancies cannot be attributed to factors other than biases in NH3 emissions. Using site measurements as constraints, we estimate that both agricultural and non-agricultural NH3 emission totals in Beijing shall increase by ∼5 times to match the observations. Future research should be performed to allocate underestimations to urban fertilizer, power, traffic, or residential sources. Dense and regular urban NH3 observations are necessary to constrain and validate bottom-up inventories and NHx simulation.

Wildfire-Derived Nitrogen Aerosols Threaten the Fragile Ecosystem in Himalayas and Tibetan Plateau.

Himalayas and Tibetan Plateau (HTP) is important for global biodiversity and regional sustainable development. While numerous studies have revealed that the ecosystem in this unique and pristine region is changing, their exact causes are still poorly understood. Here, we present a year-round (23 March 2017 to 19 March 2018) ground- and satellite-based atmospheric observation at the Qomolangma monitoring station (QOMS, 4276 m a.s.l.). Based on a comprehensive chemical and stable isotope (15N) analysis of nitrogen compounds and satellite observations, we provide unequivocal evidence that wildfire emissions in South Asia can come across the Himalayas and threaten the HTP's ecosystem. Such wildfire episodes, mostly occurring in spring (March-April), not only substantially enhanced the aerosol nitrogen concentration but also altered its composition (i.e., rendering it more bioavailable). We estimated a nitrogen deposition flux at QOMS of ∼10 kg N ha-1 yr-1, which is approximately twice the lower value of the critical load range reported for the Alpine ecosystem. Such adverse impact is particularly concerning, given the anticipated increase of wildfire activities in the future under climate change.

An unexpected catalyst dominates formation and radiative forcing of regional haze.

Although regional haze adversely affects human health and possibly counteracts global warming from increasing levels of greenhouse gases, the formation and radiative forcing of regional haze on climate remain uncertain. By combining field measurements, laboratory experiments, and model simulations, we show a remarkable role of black carbon (BC) particles in driving the formation and trend of regional haze. Our analysis of long-term measurements in China indicates declined frequency of heavy haze events along with significantly reduced SO2, but negligibly alleviated haze severity. Also, no improving trend exists for moderate haze events. Our complementary laboratory experiments demonstrate that SO2 oxidation is efficiently catalyzed on BC particles in the presence of NO2 and NH3, even at low SO2 and intermediate relative humidity levels. Inclusion of the BC reaction accounts for about 90-100% and 30-50% of the sulfate production during moderate and heavy haze events, respectively. Calculations using a radiative transfer model and accounting for the sulfate formation on BC yield an invariant radiative forcing of nearly zero W m-2 on the top of the atmosphere throughout haze development, indicating small net climatic cooling/warming but large surface cooling, atmospheric heating, and air stagnation. This BC catalytic chemistry facilitates haze development and explains the observed trends of regional haze in China. Our results imply that reduction of SO2 alone is insufficient in mitigating haze occurrence and highlight the necessity of accurate representation of the BC chemical and radiative properties in predicting the formation and assessing the impacts of regional haze.

Vehicular Emissions Enhanced Ammonia Concentrations in Winter Mornings: Insights from Diurnal Nitrogen Isotopic Signatures.

A general feature in the diurnal cycle of atmospheric ammonia (NH3) concentrations is a morning spike that typically occurs around 07:00 to 10:00 (LST). Current hypotheses to explain this morning's NH3 increase remain elusive, and there is still no consensus whether traffic emissions are among the major sources of urban NH3. Here, we confirmed that the NH3 morning pulse in urban Beijing is a universal feature, with an annual occurrence frequency of 73.0% and a rapid growth rate (>20%) in winter. The stable nitrogen isotopic composition of NH3 (δ15N-NH3) in winter also exhibited a significant diurnal variation with an obvious morning peak at 07:00 to 10:00 (-18.6‰, mass-weighted mean), higher than other times of the day (-26.3‰). This diurnal pattern suggests that a large fraction of NH3 in the morning originated from nonagricultural sources, for example, power plants, vehicles, and coal combustion that tend to have higher δ15N-NH3 emission signatures relative to agricultural emissions. In particular, the contribution from vehicular emissions increased from 18% (00:00 to 07:00) to 40% (07:00 to 10:00), while the contribution of fertilizer sources to NH3 was reduced from 15.8% at 00:00 to 07:00 to 5.2% at 07:00 to 10:00. We concluded that NH3 concentrations in winter mornings in urban Beijing were indeed enhanced by vehicle emissions, which should be considered in air pollution regulations.

Sulfate Formation Apportionment during Winter Haze Events in North China.

There is a large gap between the simulated and observed sulfate concentrations during winter haze events in North China. Although multiphase sulfate formation mechanisms have been proposed, they have not been evaluated using chemical transport models. In this study, the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) was used to apportion sulfate formation. It was found that Mn-catalyzed oxidation on aerosol surfaces was the dominant sulfate formation pathway, accounting for 92.3 ± 3.5% of the sulfate formation during haze events. Gas-phase oxidation contributed 3.1 ± 0.5% to the sulfate formation due to the low OH levels. The H2O2 oxidation in aerosol water accounted for 4.2 ± 3.6% of the sulfate formation, caused by the rapid consumption of H2O2. The contributions of O3, NO2 oxidation, and transition metal ion-catalyzed reactions in aerosol water could be negligible owing to the low aerosol water content, low pH, and high ionic strength. The contributions from in-cloud reactions were negligible due to the barrier provided by stable stratification during winter haze events.

Wall losses of oxygenated volatile organic compounds from oxidation of toluene: Effects of chamber volume and relative humidity.

Vapor wall losses can affect the yields of secondary organic aerosol. The effects of surface-to-volume (S/V) ratio and relative humidity (RH) on the vapor-wall interactions were investigated in this study. The oxygenated volatile organic compounds (OVOCs) were generated from toluene-H2O2 irradiations. The average gas to wall loss rate constant (kgw) of OVOCs in a 400 L reactor (S/V = 7.5 m-1) is 2.47 (2.41 under humid conditions) times higher than that in a 5000 L reactor (S/V = 3.6 m-1) under dry conditions. In contrast, the average desorption rate constant (kwg) of OVOCs in 400 L reactor is only 1.37 (1.20 under humid conditions) times higher than that in 5000 L reactor under dry conditions. It shows that increasing the S/V ratio can promote the wall losses of OVOCs. By contrast, the RH effect on kgw is not prominent. The average kgw value under humid conditions is almost the same as under dry conditions in the 400 L (5000 L) reactor. However, increasing RH can decrease the desorption rates. The average kwg value under dry conditions is 1.45 (1.27) times higher than that under humid conditions in the 400 L (5000 L) reactor. The high RH can increase the partitioning equilibrium timescales and enhance the wall losses of OVOCs.

Calibrations of Low-Cost Air Pollution Monitoring Sensors for CO, NO2, O3, and SO2.

Pollutant gases, such as CO, NO2, O3, and SO2 affect human health, and low-cost sensors are an important complement to regulatory-grade instruments in pollutant monitoring. Previous studies focused on one or several species, while comprehensive assessments of multiple sensors remain limited. We conducted a 12-month field evaluation of four Alphasense sensors in Beijing and used single linear regression (SLR), multiple linear regression (MLR), random forest regressor (RFR), and neural network (long short-term memory (LSTM)) methods to calibrate and validate the measurements with nearby reference measurements from national monitoring stations. For performances, CO > O3 > NO2 > SO2 for the coefficient of determination (R2) and root mean square error (RMSE). The MLR did not increase the R2 after considering the temperature and relative humidity influences compared with the SLR (with R2 remaining at approximately 0.6 for O3 and 0.4 for NO2). However, the RFR and LSTM models significantly increased the O3, NO2, and SO2 performances, with the R2 increasing from 0.3-0.5 to >0.7 for O3 and NO2, and the RMSE decreasing from 20.4 to 13.2 ppb for NO2. For the SLR, there were relatively larger biases, while the LSTMs maintained a close mean relative bias of approximately zero (e.g., <5% for O3 and NO2), indicating that these sensors combined with the LSTMs are suitable for hot spot detection. We highlight that the performance of LSTM is better than that of random forest and linear methods. This study assessed four electrochemical air quality sensors and different calibration models, and the methodology and results can benefit assessments of other low-cost sensors.

Field Evaluation of Low-Cost Particulate Matter Sensors in Beijing.

Numerous particulate matter (PM) sensors with great development potential have emerged. However, whether the current sensors can be used for reliable long-term field monitoring is unclear. This study describes the research and application prospects of low-cost miniaturized sensors in PM2.5 monitoring. We evaluated five Plantower PMSA003 sensors deployed in Beijing, China, over 7 months (October 2019 to June 2020). The sensors tracked PM2.5 concentrations, which were compared to the measurements at the national control monitoring station of the Ministry of Ecology and Environment (MEE) at the same location. The correlations of the data from the PMSA003 sensors and MEE reference monitors (R2 = 0.83~0.90) and among the five sensors (R2 = 0.91~0.98) indicated a high accuracy and intersensor correlation. However, the sensors tended to underestimate high PM2.5 concentrations. The relative bias reached -24.82% when the PM2.5 concentration was >250 µg/m3. Conversely, overestimation and high errors were observed during periods of high relative humidity (RH > 60%). The relative bias reached 14.71% at RH > 75%. The PMSA003 sensors performed poorly during sand and dust storms, especially for the ambient PM10 concentration measurements. Overall, this study identified good correlations between PMSA003 sensors and reference monitors. Extreme field environments impact the data quality of low-cost sensors, and future corrections remain necessary.

Improved Inversion of Monthly Ammonia Emissions in China Based on the Chinese Ammonia Monitoring Network and Ensemble Kalman Filter.

Ammonia (NH3) emission inventories are an essential input in chemical transport models and are helpful for policy-makers to refine mitigation strategies. However, current estimates of Chinese NH3 emissions still have large uncertainties. In this study, an improved inversion estimation of NH3 emissions in China has been made using an ensemble Kalman filter and the Nested Air Quality Prediction Modeling System. By first assimilating the surface NH3 observations from the Ammonia Monitoring Network in China at a high resolution of 15 km, our inversion results have provided new insights into the spatial and temporal patterns of Chinese NH3 emissions. More enhanced NH3 emission hotspots, likely associated with industrial or agricultural sources, were captured in northwest China, where the a posteriori NH3 emissions were more than twice the a priori emissions. Monthly variations of NH3 emissions were optimized in different regions of China and exhibited a more distinct seasonality, with the emissions in summer being twice those in winter. The inversion results were well-validated by several independent datasets that traced gaseous NH3 and related atmospheric processes. These findings highlighted that the improved inversion estimation can be used to advance our understanding of NH3 emissions in China and their environmental impacts.

Identifying Ammonia Hotspots in China Using a National Observation Network.

The limited availability of ammonia (NH3) measurements is currently a barrier to understanding the vital role of NH3 in secondary aerosol formation during haze pollution events and prevents a full assessment of the atmospheric deposition of reactive nitrogen. The observational gaps motivated us to design this study to investigate the spatial distributions and seasonal variations in atmospheric NH3 on a national scale in China. On the basis of a 1-year observational campaign at 53 sites with uniform protocols, we confirm that abundant concentrations of NH3 [1 to 23.9 µg m-3] were identified in typical agricultural regions, especially over the North China Plain (NCP). The spatial pattern of the NH3 surface concentration was generally similar to those of the satellite column concentrations as well as a bottom-up agriculture NH3 emission inventory. However, the observed NH3 concentrations at urban and desert sites were comparable with those from agricultural sites and 2-3 times those of mountainous/forest/grassland/waterbody sites. We also found that NH3 deposition fluxes at urban sites account for only half of the emissions in the NCP, suggesting the transport of urban NH3 emissions to downwind areas. This finding provides policy makers with insights into the potential mitigation of nonagricultural NH3 sources in developed regions.

PM2.5 levels, chemical composition and health risk assessment in Xinxiang, a seriously air-polluted city in North China.

Seventeen PM2.5 samples were collected at Xinxiang during winter in 2014. Nine water-soluble ions, 19 trace elements and eight fractions of carbonaceous species in PM2.5 were analyzed. PM2.5 concentrations and elements species during different periods with different pollution situations were compared. The threat of heavy metals in PM2.5 was assessed using incremental lifetime cancer risk. During the whole period, serious regional haze pollution persisted, and the averaged concentration of PM2.5 was 168.5 µg m-3, with 88.2 % of the daily samples exhibiting higher PM2.5 concentrations than the national air quality standard II. The high NO3-/SO42- ratio suggested that vehicular exhaust made an important contribution to atmospheric pollution. All of organic carbon and elemental carbon ratios in this study were above 2.0 for PM2.5, which might reflect the combined contributions from coal combustion, motor vehicle exhaust and biomass burning. Mean 96-h backward trajectory clusters indicated that more serious air pollution occurred when air masses transported from the Hebei, Shanxi and Zhengzhou. The concentrations of the water-soluble ions and trace elements on haze days were 2 and 1.8 times of those on clear days. The heavy metals in PM2.5 might not cause non-cancerous health issues by exposure through the human respiratory system. However, lifetime cancer risks of heavy metals obviously exceeded the threshold (10-6) and might have a cancer risk for residents in Xinxiang. This study provided detailed composition data and comprehensive analysis of PM2.5 during the serious haze pollution period and their potential impact on human health in Xinxiang.

Typical atmospheric haze during crop harvest season in northeastern China: A case in the Changchun region.

This study presents the mass concentrations of PM2.5, O3, SO2 and NOx at one urban, one suburban and two rural locations in the Changchun region from September 25 to October 27 2013. Major chemical components of PM2.5 at the four sites were daily sampled and analyzed. Most of daily concentrations of SO2 (7-82µg/m3), O3 (27-171µg/m3) and NOx (14-213µg/m3) were below the limits of the National Ambient Air Quality Standard (NAAQS) in China. However, PM2.5 concentrations (143-168µg/m3) were 2-fold higher than NAAQS. Higher PM2.5 concentrations (~150µg/m3) were measured during the pre-harvest and harvest at the urban site, while PM2.5 concentrations significantly increased from 250 to 400µgm-3 at suburban and rural sites with widespread biomass burning. At all sites, PM2.5 components were dominated by organic carbon (OC) and followed by soluble component sulfate (SO42-), ammonium (NH4+) and nitrate (NO3-). Compared with rural sites, urban site had a higher mineral contribution and lower potassium (K+ and K) contribution to PM2.5. Severe atmospheric haze events that occurred from October 21 to 23 were attributed to strong source emissions (e.g., biomass burning) and unfavorable air diffusion conditions. Furthermore, coal burning originating from winter heating supply beginning on October 18 increased the atmospheric pollutant emissions. For entire crop harvest period, the Positive Matrix Factorization (PMF) analysis indicated five important emission contributors in the Changchun region, as follows: secondary aerosol (39%), biomass burning (20%), supply heating (18%), soil/road dust (14%) and traffic (9%).

Modifications to the azide method for nitrate isotope analysis.

RATIONALE: The azide method for measuring the stable isotope ratios of nitrate (NO3- ) is easy to set up. However, the method requires spongy cadmium (Cd) or activated Cd powder which are not easy to prepare, and a toxic azide buffer is used. We aimed to use Cd powder directly to simplify preparation and to substantially reduce the azide dose. METHODS: The reaction conditions were optimized in order to maximize the NO3- reduction yield. The original azide buffer was diluted by 10- to 10000-fold with or without addition of sodium acetate to reduce O-exchange between nitrite (NO2- ) and H2 O. The isotope ratios of the produced nitrous oxide (N2 O), used to examine the overall reaction performance, were measured using a purge and cryogenic trap system coupled to an isotope ratio mass spectrometer. RESULTS: It was found that Cd powder could be directly used to reduce NO3- to NO2- . A 100-fold diluted azide buffer could be used to reduce NO2- to N2 O when only the δ15 N value was measured, and the diluted azide buffer with sodium acetate when both δ15 N and δ18 O values were measured. Using the modified method, the standard deviations of the δ15 N and δ18 O measurements of international NO3- standards were 0.1 to 1.0‰ and often better than 0.3‰ (3 replicates). CONCLUSIONS: Compared with the original azide method, the techniques described here can reduce preparation time by using Cd powder without activation in the first reaction step and substantially (by >60-fold) reduce the dose of extremely toxic reagents containing azide by incorporating sodium acetate in the second reaction step. Our modified method is suitable for samples with small volume (5 mL), being different from previous methods in which 50 or 70 mL samples were used. Copyright © 2016 John Wiley & Sons, Ltd.

Fossil Fuel Combustion-Related Emissions Dominate Atmospheric Ammonia Sources during Severe Haze Episodes: Evidence from (15)N-Stable Isotope in Size-Resolved Aerosol Ammonium.

The reduction of ammonia (NH3) emissions is urgently needed due to its role in aerosol nucleation and growth causing haze formation during its conversion into ammonium (NH4(+)). However, the relative contributions of individual NH3 sources are unclear, and debate remains over whether agricultural emissions dominate atmospheric NH3 in urban areas. Based on the chemical and isotopic measurements of size-resolved aerosols in urban Beijing, China, we find that the natural abundance of (15)N (expressed using δ(15)N values) of NH4(+) in fine particles varies with the development of haze episodes, ranging from -37.1‰ to -21.7‰ during clean/dusty days (relative humidity: ∼ 40%), to -13.1‰ to +5.8‰ during hazy days (relative humidity: 70-90%). After accounting for the isotope exchange between NH3 gas and aerosol NH4(+), the δ(15)N value of the initial NH3 during hazy days is found to be -14.5‰ to -1.6‰, which indicates fossil fuel-based emissions. These emissions contribute 90% of the total NH3 during hazy days in urban Beijing. This work demonstrates the analysis of δ(15)N values of aerosol NH4(+) to be a promising new tool for partitioning atmospheric NH3 sources, providing policy makers with insights into NH3 emissions and secondary aerosols for regulation in urban environments.

Chemical method for nitrogen isotopic analysis of ammonium at natural abundance.

We report a new chemical method to determine the (15)N natural abundance (δ(15)N) for ammonium (NH4(+)) in freshwater (e.g., precipitation) and soil KCl extract. This method is based on the isotopic analysis of nitrous oxide (N2O). Ammonium is initially oxidized to nitrite (NO2(-)) by hypobromite (BrO(-)) using previously established procedures. NO2(-) is then quantitatively converted into N2O by hydroxylamine (NH2OH) under strongly acid conditions. The produced N2O is analyzed by a commercially available purge and cryogenic trap system coupled to an isotope ratio mass spectrometer (PT-IRMS). On the basis of a typical analysis size of 4 mL, the standard deviation of δ(15)N measurements is less than 0.3‰ and often better than 0.1‰ (3 to 5 replicates). Compared to previous methods, the technique here has several advantages and the potential to be used as a routine method for (15)N/(14)N analysis of NH4(+): (1) substantially simplified preparation procedures and reduced preparation time particularly compared to the methods in which diffusion or distillation is involved since all reactions occur in the same vial and separation of NH4(+) from solution is not required; (2) more suitability for low volume samples including those with low N concentration, having a blank size of 0.6 to 2 nmol; (3) elimination of the use of extremely toxic reagents (e.g., HN3) and/or the use of specialized denitrifying bacterial cultures which may be impractical for many laboratories.

Oligomer formation from cross-reaction of Criegee intermediates in the styrene-isoprene-O3 mixed system.

Alkene ozonolysis can produce stabilized Criegee intermediates (SCIs), which play a key role in oligomers' formation. Though styrene and isoprene coexist in the ambient atmosphere as important anthropogenic and biogenic secondary organic aerosol (SOA) precursors, respectively, their cross-reactions have not received attention. This study investigated the interactions of SCIs from styrene and isoprene ozonolysis for the first time. The high-resolution Orbitrap mass spectrometer was used to determine the unique ion mass spectra of the isoprene-styrene-O3 mixture. The results show that the signal intensities of new ions account for >8.4% of total ions in the mass spectra of the styrene-isoprene-O3 mixed system. Styrene and isoprene ozonolysis can produce characteristic C7-SCI and C4-SCI, respectively. C7-SCI and C4-SCI can be involved in the cross-reactions, and the results of tandem mass spectra directly confirmed both C7-SCI and C4-SCI as chain units. The O/C and H/C ratios of cross-products are in the range of 0.38-1.07 and 1.00-1.50, respectively, which are consistent with cross-reaction products. Adding a C7-SCI unit reduces the oligomer's volatility by 1.3-1.4 orders of magnitude lower than adding a C4-SCI unit. Thus, C4-SCI can compete with C7-SCI to react with styrene-derived RO2/RC(O)OH to produce more volatile cross-products, while the less volatile cross-products can be formed when isoprene-derived RO2/RC(O)OH reacted with C7-SCI instead of C4-SCI. The SOA yield of the mixed system is lower than that of the single styrene-O3 system but higher than that of the single isoprene-O3 system. Ambient particles were also collected, and 5 possible SCI-related cross-products were identified. This study illustrates the effects of SCI-related cross-reactions on SOA components and physicochemical properties, providing a basis for future research on SCI-related cross-reactions that frequently occur in the ambient atmosphere.