Average Mixing Ratio Research Articles

Vertical Distribution of Water Vapor During Haze Processes in Northeast China Based on Raman Lidar Measurements

Haze refers to an atmospheric phenomenon with extremely low visibility, which has significant impacts on human health and safety. Water vapor alters the scattering properties of atmospheric particulate matter, thus affecting visibility. A comprehensive analysis of the role of water vapor in haze formation is of great scientific significance for forecasting severe pollution weather events. This study investigates the distribution characteristics and variations of water vapor during haze weather in Changchun City (44°N, 125.5°E) in autumn and winter seasons, aiming to reveal the relationship between haze and atmospheric water vapor content. Analysis of observational results for a period of two months (October to November 2023) from a three-wavelength Raman lidar deployed at the site reveals that atmospheric water vapor content is mainly concentrated below 5 km, accounting for 64% to 99% of the total water vapor below 10 km. Furthermore, water vapor content in air pollution exhibits distinct stratification characteristics with altitude, especially within the height range of 1–3 km, where significant water vapor variation layers exist, showing spatial consistency with inversion layers. Statistical analysis of haze events at the site indicates a high correlation between the concentration variations of PM2.5 and PM10 and the variations in average water vapor mixing ratio (WVMR). During haze episodes, the average WVMR within 3 km altitude is 3–4 times higher than that during clear weather. Analysis of spatiotemporal height maps of aerosols and water vapor during a typical haze event suggests that the relative stability of the atmospheric boundary layer may hinder the vertical transport and diffusion of aerosols. This, in turn, could lead to a sharp increase in aerosol extinction coefficients through hygroscopic growth, thereby possibly exacerbating haze processes. These observational findings indicate that water vapor might play a significant role in haze formation, emphasizing the potential importance of observing the vertical distribution of water vapor for better simulation and prediction of haze events.

Ambient volatile organic compounds in a typical industrial city in southern China: Impacts of aromatic hydrocarbons from new industry

New industrial parks, including fine chemical, medical manufacturers, etc., are emerging in modern cities in China, whereas their emissions and impacts have not been fully illuminated. In this study, ambient volatile organic compounds (VOCs) in Huizhou were measured in three functional zones, namely new industrial, roadside, and residential zones. The average mixing ratios of total VOCs were as follow: industrial (56.22 ± 15.06 ppbv) > roadside (39.30 ± 12.96 ppbv) > residential (26.03 ± 7.31 ppbv). The ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAP) of VOCs in the industrial zone were 1.5–2.3 and 1.7–3.1 times those in the other zones, respectively. Aromatics contributed the most to OFP (39.8 % - 44.8 %) and SOAP (78.9 % - 91.0 %), with much less contributions to VOCs mixing ratios (18.3 % - 21.2 %). Naphthalene was the most abundant aromatic species across the three zones and ranked among the top contributors to OFP and SOAP among all VOCs species. Source apportionment identified that new industrial emissions and solvent use was the largest VOCs contributor in the industrial zone (53.9 %), traffic-related emissions dominated in the roadside zone (40.7 %), while new industrial and traffic-related emissions contributed similar in the residential zone (32.9 % and 34.7 %, respectively). The carcinogenic and non-carcinogenic risks of hazardous VOCs were above the acceptable threshold, primarily due to new industrial and traffic-related emissions. Our results suggested to strengthen the control of new industrial emissions and aromatics sources in Huizhou city to improve air quality and protect human health.

TROPOMI unravels transboundary transport pathways of atmospheric carbon monoxide in Tibetan Plateau

Numerous studies have reported in situ monitoring and source analysis in the Tibetan Plateau (TP), a region crucial for climate systems. However, a gap remains in understanding the comprehensive distribution of atmospheric pollutants in the TP and their transboundary pollution transport. Here, we analyzed the high-resolution satellite TROPOMI observations from 2018 to 2023 in Tibet and its surrounding areas. Our result reveals that, contrary to the results from in situ surface CO monitoring, Tibet exhibits a distinct seasonality in atmospheric carbon monoxide total column average mixing ratio (XCO), with higher levels in summer and lower levels in winter. This distinctive seasonal pattern may be related to the TP's ‘air pump’ effect and the Asia summer monsoon. Before 2022, the annual growth rate of XCO in Tibet was 1.63 %·year−1; however, it declined by 6.88 % in 2022. Source analysis and satellite observations suggest that CO from South Asia may enter Tibet either by crossing the Himalayas or through the Yarlung Zangbo Grand Canyon. We discovered that spring outbreaks of open biomass burning (OBB) in South and Southeast Asia led to an 11.57–27.98 % increase in XCO over Tibet. Favorable wind pattern and unique topography of the canyon promote the high concentrations CO transport to Tibet. Our greater concern is whether the TP will experience more severe transboundary pollution in the future.

Atmospheric NH3 in urban Beijing: long-term variations and implications for secondary inorganic aerosol control

Abstract. Ammonia (NH3) has major effects on the environment and climate. In situ measurements of NH3 concentrations taken between June 2009 and July 2020 at an urban site in Beijing were analyzed to study its long-term behavior, responses to meteorological conditions, and influences on the formation of secondary inorganic aerosols (SIAs). The 11-year average NH3 mixing ratio was 26.9±19.3 ppb (median 23.5 ppb). The annual average NH3 mixing ratio increased from 2009 to 2017 by 50 % and then decreased by 49 % from 2017 to 2020. Notably, the long-term trend for NH3 at the ground level did not align with the trends derived from satellite observations and emission estimates. The NH3 concentration exhibited a stronger correlation with the daily variation in water vapor (H2O) concentration than with air temperature. Thermodynamic modeling revealed the nonlinear response of SIAs to NH3, with increased sensitivity when its concentration was reduced to 40 % of the initial level. Although reducing NH3 concentrations can improve air quality during winter, controlling acid gas concentrations has a greater effect than controlling NH3 concentrations on reducing SIA concentrations, until NH3 and acidic gas concentrations are reduced below 80 % of their current levels. Nevertheless, the increased mass proportion of ammonium salts in SIAs during the observation period indicates that future control measures for NH3 concentrations may need to be prioritized in Beijing.

Spatial mapping of greenhouse gases using a UAV monitoring platform over a megacity in China

Urban environments are recognized as main anthropogenic contributors to greenhouse gas (GHG) emissions, characterized by unevenly distributed emission sources over the urban environments. However, spatial GHG distributions in urban regions are typically obtained through monitoring at only a limited number of locations, or through model studies, which can lead to incomplete insights into the heterogeneity in the spatial distribution of GHGs. To address such information gap and to evaluate the spatial representation of a planned GHG monitoring network, a custom-developed atmospheric sampler was deployed on a UAV platform in this study to map the CO2 and CH4 mixing ratios in the atmosphere over Zhengzhou in central China, a megacity of nearly 13 million people. The aerial survey was conducted along the main roads at an altitude of 150 m above ground, covering a total distance of 170 km from the city center to the suburbs. The spatial distributions of CO2 and CH4 mixing ratios in Zhengzhou exhibited distinct heterogeneities, with average mixing ratios of CO2 and CH4 at 439.2 ± 10.8 ppm and 2.12 ± 0.04 ppm, respectively. A spatial autocorrelation analysis was performed on the measured GHG mixing ratios across the city, revealing a spatial correlation range of approximately 2 km for both CO2 and CH4 in the urban area. Such a spatial autocorrelation distance suggests that the urban GHG monitoring network designed for emission inversion purposes need to have a spatial resolution of 4 km to characterize the spatial heterogeneities in the GHGs. This UAV-based measurement approach demonstrates its capability to monitor GHG mixing ratios across urban landscapes, providing valuable insights for GHG monitoring network design.

Ethylene Oxide in Southeastern Louisiana's Petrochemical Corridor: High Spatial Resolution Mobile Monitoring during HAP-MAP.

Ethylene oxide ("EtO") is an industrially made volatile organic compound and a known human carcinogen. There are few reliable reports of ambient EtO concentrations around production and end-use facilities, however, despite major exposure concerns. We present in situ, fast (1 Hz), sensitive EtO measurements made during February 2023 across the southeastern Louisiana industrial corridor. We aggregated mobile data at 500 m spatial resolution and reported average mixing ratios for 75 km of the corridor. Mean and median aggregated values were 31.4 and 23.3 ppt, respectively, and a majority (75%) of 500 m grid cells were above 10.9 ppt, the lifetime exposure concentration corresponding to 100-in-one million excess cancer risk (1 × 10-4). A small subset (3.3%) were above 109 ppt (1000-in-one million cancer risk, 1 × 10-3); these tended to be near EtO-emitting facilities, though we observed plumes over 10 km from the nearest facilities. Many plumes were highly correlated with other measured gases, indicating potential emission sources, and a subset was measured simultaneously with a second commercial analyzer, showing good agreement. We estimated EtO for 13 census tracts, all of which were higher than EPA estimates (median difference of 21.3 ppt). Our findings provide important information about EtO concentrations and potential exposure risks in a key industrial region and advance the application of EtO analytical methods for ambient sampling and mobile monitoring for air toxics.

Seasonal variability of volatile organic compounds (VOCs) at a high-altitude station in the Western Ghats, India: Influence of biogenic, anthropogenic emissions and long-range transport

Seasonal variability of volatile organic compounds (VOCs) was studied using year-long observations (June 2019–May 2020) over a high-altitude (1380m AMSL) forested site in the Western Ghats of India. Isoprene, a well-known biogenic VOC, peaked during pre-monsoon. Temperature stress and higher photo synthetically active radiation (PAR) were the drivers behind isoprene emissions from the surrounding forested regions. The daytime average isoprene mixing ratio was 1.92 ± 1.51 ppb during summer and the night time average was 0.02 ± 0.01 ppb. A strong relationship between isoprene mixing ratio and ambient temperature was derived. Most of the anthropogenic VOCs like acetonitrile, benzene, toluene and xylene were found to be higher during winter. These anthropogenic VOCs mostly exhibited afternoon to evening peaks, which suggests the contribution by traffic emissions along with other combustion sources (biofuels) and vertical updraft of pollutants from the surrounding valley region. The toluene to benzene ratio (T/B) was >1 during the afternoon and evening hours in monsoon, whereas, aged air masses with lower T/B ratios (<0.7) prevailed during other seasons. Polar bi-variate plots reveal that toluene, xylene and tri-methyl benzene (TMB) were mostly emitted at the south-west of the measurement site, irrespective of the season, indicating a dominant local traffic related source throughout the year. The contribution of local emissions and regional background on two selected aromatic VOCs, toluene and xylene was estimated, revealing the dominance of local anthropogenic sources during monsoon and post monsoon. Positive matrix factorization revealed three source factors in all the seasons with one additional factor during winter and pre-monsoon. The first factor was constituted of toluene, benzene, xylene and TMB, and the T/B ratio was ∼1.2, indicating traffic/fossil fuel contribution. A second ‘biomass burning’ factor was dominated by acetonitrile, ethanal, acetone, and benzene in which the T/B ratio was 0.45. Factors one & two were further validated by comparison with chamber experiments conducted using different combustion sources and solvents. The third factor was dominated by isoprene and monoterpenes which were attributed to biogenic emissions. The fourth factor comprised mainly of acetonitrile, ethanal, and acetone indicating aged air masses due to long-range transport with contributions from photochemical production and biomass burning.

Representative High-Temperature Hydrothermal Activities in the Himalaya Geothermal Belt (HGB): A Review and Future Perspectives

Southern Tibet and western Yunnan are areas with an intensive distribution of high-temperature geothermal systems in China, as an important part of the Himalayan Geothermal Belt (HGB). In recent decades, China has conducted systematic research on high-temperature geothermal fields such as Yangbajing, Gudui, and Rehai. However, a comprehensive understanding has not yet been formed. The objective of this study was to enhance comprehension of the high-temperature geothermal system in the HGB and to elucidate the hydrogeochemical characteristics of geothermal fluids. This will facilitate the subsequent sustainable development and exploitation of domestic high-temperature hydrothermal geothermal resources. To this end, this study analysed geothermal spring and borehole data from the Yangbajing, Gudui, and Rehai geothermal fields. Based on previous research results, the source, evolution, and reservoir temperature characteristics of geothermal fluids are compared and summarised. The main high-temperature geothermal water in the geothermal field is derived from the deep Cl-Na geothermal fluid. Yangbajing’s and Gudui’s geothermal waters are primarily recharged by snow-melt water, while Rehai’s geothermal water is mainly recharged by local meteoric water. The average mixing ratios of magmatic water in the Yangbajing, Gudui, and Rehai geothermal fields are 17%, 21%, and 22%, respectively. The Yangbajing and Gudui geothermal fields have a relatively closed geological environment, resulting in a stronger water–rock interaction compared to the Rehai geothermal field. As geothermal water rises, it mixes with shallow cold water infiltration. The mixing ratios of cold water in the Yangbajing, Gudui, and Rehai geothermal fields are 60–70%, 40–50%, and 20–40%, respectively. Based on the solute geothermometer calculations, the maximum geothermal reservoir temperatures for Yangbajing, Gudui, and Rehai are 237 °C, 266 °C, and 282 °C, respectively. This study summarises and compares the hydrogeochemical characteristics of three typical high-temperature geothermal fields. The findings provide an important theoretical basis for the development of high-temperature geothermal resources in the Himalayan Geothermal Belt.

Vertical Characteristics of HCHO and NO2 in Suburban Shanghai: Understanding of Ozone formation sensitivity via Secondary HCHO

Abstract Since ozone (O3) pollution in China is on the rise, vertical distribution of nitrogen dioxide (NO2) and formaldehyde (HCHO) and their role towards O3 formation are critical towards designing O3 control strategies. Seasonal characteristics of aerosols, HCHO and NO2 were investigated over suburban Shanghai using Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) from June 2020 to May 2021. For HCHO, the highest average vertical mixing ratios (VMRs) were observed for summer (0.775 ppb), followed by autumn (0.719 ppb), spring (0.718 ppb) and winter (0.672 ppb) at ground level. Seasonal trends in NO2 VMRs were observed to be opposite to that of HCHO with peak values occurring during winter (2.212 ppb) at the ground level followed by autumn (1.881 ppb), spring (1.415 ppb) and summer (1.124 ppb). In vertical, aerosols depicted a Gaussian shape with a higher values between 0.2 - 0.5 km. An exponential decay in NO2 VMRs is observed from 0.0 km to 3.0 km while the integral component of HCHO was found to be concentrated up to 2.0 km particularly during summer months. The vertical distribution of NO2 in different seasons mainly appeared below 0.5 km, while that of HCHO appeared within the range of 0.2-1.0 km. Both aerosols and NO2 tend to be higher during haze days compared to non-haze days while HCHO was found to be higher during clear days owing to high photochemical activity on a clear day. Based on the ratio of HCHO to NO2 (RFN), this study attempted to quantify the vertical characteristics of O3 sensitivity for different seasons. The results indicated that the O3 sensitivity was VOC-limited both at lower (generally, 0.0 - 0.6 km) and higher heights (1.8 - 3.0 km) while some transition limited scenarios were found at middle height (0.7 – 1.7 km) particularly during daytime. The results depicted that secondary HCHO is a crucial factor controlling on O3 sensitivity over Shanghai where enhanced ratio of VOC limited regime was observed with secondary HCHO for all the seasons.

Significant Impact of Reactive Chlorine on Complex Air Pollution Over the Yangtze River Delta Region, China

AbstractThe chlorine radical (Cl) plays a crucial role in the formation of secondary air pollutants by determining the total atmospheric oxidative capacity (AOC). However, there are still large discrepancies among studies on chlorine chemistry, mainly due to uncertainties from three aspects: (a) Anthropogenic emissions of reactive chlorine species from disinfectant usage are typically overlooked. (b) The heterogeneous reaction uptake coefficients used in air quality models resulted in certain differences. (c) The co‐effect of anthropogenic and natural emissions is rarely investigated. In this study, the Weather Research and Forecasting (WRF)‐Community Multiscale Air Quality (CMAQ) modeling system (updated with 21 new reactions and a comprehensive emissions inventory) was used to simulate the combined impact of chlorine emissions on the air quality of a coastal city cluster in the Yangtze River Delta (YRD) region. The results indicate that the new emissions of reactive chlorine and the updated gas‐phase and heterogeneous chlorine chemistry can significantly enhance the AOC by 21.3%, 8.7%, 43.3%, and 58.7% in spring, summer, autumn, and winter, respectively. This is more evident in inland areas with high Cl concentrations. Our updates to the chlorine chemistry also increases the monthly mean maximum daily 8‐hr average (MDA 8) O3 mixing ratio by 4.1–7.0 ppbv in different seasons. Additionally, chlorine chemistry promotes the formation of fine particulate matter (PM2.5), with maximum monthly average enhancements of 4.7–13.3 μg/m3 in different seasons. This study underlines the significance of adding full chlorine emissions and updating chlorine chemistry in air quality models, and demonstrates that chlorine chemistry may significantly impact air quality over coastal regions.

Primary sources of HONO vary during the daytime: Insights based on a field campaign

Nitrous acid (HONO) is an established precursor of hydroxyl (OH) radical and has significant impacts on the formation of PM2.5 and O3. Despite extensive research on HONO observation in recent years, knowledge regarding its sources and sinks in urban areas remains inadequate. In this study, we monitored the atmospheric concentrations of HONO and related pollutants, including gaseous nitric acid and particulate nitrate, simultaneously at a supersite in downtown Chengdu, a megacity in southwestern China during spring, when was chosen due to its tolerance for both PM2.5 and O3 pollution. Furthermore, we employed the random forest model to fill the missing data of HONO, which exhibited good predictive performance (R2 = 0.96, RMSE = 0.36 ppbv). During this campaign, the average mixing ratio of HONO was measured to be 1.0 ± 0.7 ppbv. Notably, during periods of high O3 and PM2.5 concentrations, the mixing ratio of HONO was >50 % higher compared to the clean period. We developed a comprehensive parameterization scheme for the HONO budget, and it performed well in simulating diurnal variations of HONO. Based on the HONO budget analysis, we identified different mechanisms that dominate HONO formation at different times of the day. Vehicle emissions and NO2 heterogeneous conversions were found to be the primary sources of HONO during nighttime (21.0 %, 30.2 %, respectively, from 18:00 to 7:00 the next day). In the morning (7:00–12:00), NO2 heterogeneous conversions and the reaction of NO with OH became the main sources (35.0 %, 32.2 %, respectively). However, in the afternoon (12:00–18:00), the heterogeneous photolysis of HNO3 on PM2.5 was identified as the most substantial source of HONO (contributing 52.5 %). This study highlights the significant variations in primary HONO sources throughout the day.

Spatio-seasonal characterization and emissions estimation of ozone-depleting substances in the Pearl River Delta, China

Although chlorofluorocarbons (CFCs), CH3Br and chlorinated solvents such as CH3Cl3 and CCl4 have been entirely phased out in the Pearl River Delta (PRD) region, these compounds still exist chronically in atmosphere. In this study, ambient air samples were collected at twenty sites in the PRD region in winter (November to December 2019) and summer (August 2020) to characterize the spatio-seasonal variation of ozone-depleting substances (ODS), including CFC-11, CFC-12, CFC-113, CFC-114, CH3CCl3, CCl4, and CH3Br, and to estimate their emissions. Our observation showed that the average mixing ratios of the target ODS in the PRD region were 16.5%–92.5% lower compared with their reported levels in 2001 except for CFC-114, which basically remained at a constant level. Among the seven ODS, the average mixing ratio of CH3CCl3 declined most rapidly. The mixing ratios of the target ODS were higher in summer than in winter. Higher mixing ratios of the target ODS were observed in the two PRD urban background sites than the northern hemisphere background level, suggesting the existence of local emission sources. The spatial distribution indicated that the Foshan–Guangzhou–Dongguan–Shenzhen corridor area had the highest mixing ratios of the target ODS. Based on the CO-tracer ratio method, the estimated emissions of CFC-11, CFC-12, CFC-113, CFC-114, CH3Br, CH3CCl3 and CCl4 were 1.2, 0.8, 0.3, 0.2, 0.1, 0.1 and 0.4 kt/year, respectively. CFCs showed a very slow reduction in emission since 2008 in general, and the estimated emissions of CH3CCl3 and CCl4 gradually declined from the high value reported in 2004 while CH3Br kept the same level. The findings of this study can help to get a better understanding of the emissions status of ODS in the PRD region and provide valuable information for further reduction processes.

Chloramines as an important photochemical source of chlorine atoms in the urban atmosphere

Monochloramine, dichloramine and trichloramine (NH2Cl, NHCl2, NCl3) are measured in the ambient atmosphere, in downtown Toronto in summer (median 39, 15 and 2.8 ppt) and winter (median 11, 7.3 and 0.7 ppt). NCl3 and NHCl2 were also measured in summer (median 1.3 and 14 ppt) from a suburban Toronto location. Measurements at two locations demonstrate prevalence of chloramines in an urban atmosphere. At both sites, NCl3 exhibits a strong diel pattern with maximum values during the night, and photolytic loss with sunrise. At the downtown site, a strong positive correlation between NH2Cl and NHCl2 in the summer night indicates a common source, with daily average peak mixing ratios approaching 500 and 250 ppt, respectively. As a previously unidentified source of chlorine (Cl) atoms, we demonstrate that NCl3 photolysis contributes 49 to 82% of the total local summertime Cl production rate at different times during the day with an average noontime peak of 3.8 × 105 atoms/cm3/s, with smaller contributions from ClNO2 and Cl2. Photolysis of NH2Cl and NHCl2 may augment this Cl production rate. Our measurements also demonstrate a daytime enhancement of chloroacetone in both the summer and winter, demonstrating the importance of Cl photochemistry. The results suggest that chloramines are an important source of Cl atoms in urban areas, with potential impacts on the abundance of organic compounds, ozone, nitrogen oxides, and particulate matter. Future studies should explore the vertical gradients of chloramines and their contribution to Cl production throughout the boundary layer.

VOC species controlling O3 formation in ambient air and their sources in Kaifeng, China

The concentration of ozone has been in a rising crescendo in the last decade while the fine particles (PM2.5) is gradually decreasing but still at a high level in central China. Volatile organic compounds (VOCs) are the vital precursors of ozone and PM2.5. A total of 101 VOC species were measured in four seasons at five sites from 2019 to 2021 in Kaifeng. VOC sources and geographic origin of sources were identified by the positive matrix factorization (PMF) model and the hybrid single-particle Lagrangian integrated trajectory transport model. The source-specific OH loss rates (LOH) and ozone formation potential (OFP) were calculated to estimate the effects of each VOC source. The average mixing ratios of total VOCs (TVOC) were 43.15 parts per billion (ppb), of which the alkanes, alkenes, aromatics, halocarbons, and oxygenated VOCs respectively accounted for 49%, 12%, 11%, 14%, and 14%. Although the mixing ratios of alkenes were comparatively low, they played a dominant role in the LOH and OFP, especially ethene (0.55 s−1, 7%; 27.11 μg/m3, 10%) and 1,3-butadiene (0.74 s−1, 10%; 12.52 μg/m3, 5%). The vehicle-related source which emitted considerable alkenes ranked as the foremost contributing factor (21%). Biomass burning was probably influenced by other cities in the western and southern Henan and other provinces, Shandong and Hebei.

Variation Characteristics and Ozone Formation Potential of Ambient VOCs in Urban Beijing in Summer

To further understand the effect of volatile organic compounds (VOCs) on ozone (O3) formation in seasons when ozone (O3) pollution occurs frequently, the variation in VOCs, chemical composition characteristics, and ozone formation potential (OFP) were studied, using high-resolution online monitoring data obtained in an urban site of Beijing in the summer of 2019. The results showed that the averaged total mixing ratio of VOCs was (25.12±10.11)×10-9, with alkanes as the most abundant group (40.41%), followed by oxygenated volatile organic compounds (OVOCs) (25.28%) and alkenes/alkynes (12.90%). The diurnal variation in VOCs concentration showed a bimodal pattern with the morning peak appearing from 06:00 to 08:00, when the proportion of alkenes/alkynes increased significantly,indicating that the vehicle exhaust contributed more to VOCs. The VOCs concentration decreased in the afternoon when the proportion of OVOCs showed an upward trend, and the photochemical reaction and meteorological factors had great influences on VOCs concentration and composition.The OFP in urban Beijing in summer was 154.64 μg·m-3; aromatics, OVOCs, and alkenes/alkynes played dominant roles in OFP; and hexanal, ethylene, and m/p-xylene were the key species. The results suggested the need for the control of vehicle and solvent use and restaurants emissions to reduce the high level of O3in urban Beijing in summer. The diurnal variations in ethane/acetylene (E/E) and m/p-xylene/ethylbenzene (X/E) showed that the photochemical-aging of the air masses was obvious, which was jointly affected by photochemical reactions and regional transport. The back-trajectory results indicated a high contribution of southeastern and southwestern air masses to atmospheric alkanes and OVOCs concentration; moreover, aromatics and alkenes were mainly from local sources.

Update on SO2, detection of OCS, CS, CS2, and SO3, and upper limits of H2S and HOCl in the Venus mesosphere using SOIR on board Venus Express

We report on the update of SO2 and first detections of SO3, CS, and CS2, and detection of OCS above the cloud deck using the SOIR instrument on-board Venus Express, and upper limit profiles of H2S and HOCl. Based on the solar occultation spectra measured by SOIR covering all latitudes over the 2006–2014 period, we find an average SO2 volume mixing ratio of ∼0.02 ppm below 90 km which increases to 5 ppm at 100 km; average OCS abundance of 1 ppb to 1 ppm between 65 and 100 km increasing with altitude; mean SO3 values of 0.1 ppm at 75 km, 1 ppm at 85 km, and 10 ppm at 95 km; CS volume mixing ratios varying from 0.1 ppm at 65 km to 40 ppm at 100 km; finally we report 0.03 ppm of CS2 at 70 km and 5 ppm at 90 km. It is important to note the detections for all of these species may be biased to higher volume mixing ratios at higher altitudes based on the detection limits for SOIR. Upper-limits for H2S and HOCl are determined. All abundances show large variabilities with time and/or latitude equal to at least one order of magnitude at all altitudes. We also study the detection statistics of all detected species as a function of time, latitude, and side of the terminator.

Seasonal and Diurnal Variability of Monoterpenes in the Eastern Mediterranean Atmosphere

Monoterpenes significantly affect air quality and climate as they participate in tropospheric ozone formation, new particle formation (NPF), and growth through their oxidation products. Vegetation is responsible for most biogenic volatile organic compound (BVOC) emissions released into the atmosphere, yet the contribution of shrub and regional transport to the ambient monoterpene mixing ratios is not sufficiently documented. In this study, we present one-year systematic observations of monoterpenes in the Eastern Mediterranean at a remote coastal site, affected mainly by the typical phrygana vegetation found on the Island of Crete in Greece. A total of 345 air samples were collected in absorption tubes and analyzed by a GC-FID system during three intensive campaigns (in spring 2014, summer 2014, and spring 2015) in addition to the systematic collection of one diurnal cycle per week from October 2014 to April 2015. Limonene, α-pinene and 1,8-cineol have been detected. The mixing ratios of α-pinene during spring and summer show a cycle that is typical for biogenic compounds, with high levels during the night and early morning, followed by an abrupt decrease around midday, which results from the strong photochemical depletion of this compound. Limonene was the most abundant monoterpene, with average mixing ratios of 36.3 ± 66 ppt. The highest mixing ratios were observed during autumn and spring, with a maximum mixing ratio in the early afternoon. The spring and autumn maxima could be attributed to the seasonal behavior of vegetation growth at Finokalia. The green period starts in late autumn when phrygana vegetation grows because of the rainfall; the temperature is still high at this time, as Finokalia is located in the southeast part of Europe. Statistical analyses of the observations showed that limonene and α-pinene have different sources, and none of the studied monoterpenes is correlated with the anthropogenic sources. Finally, the seasonality of the new particle formation (NPF) events and monoterpene mixing ratios show similarities, with a maximum occurring in spring, indicating that monoterpenes may contribute to the production of new particles.

Spatial characterization of HCHO and reapportionment of its secondary sources considering photochemical loss in Taiyuan, China

Formaldehyde (HCHO) plays an important role in atmospheric ozone (O3) formation. To accurately identify the sources of HCHO, carbonyls and volatile organic compounds (VOCs) were measured at three urban sites (Taoyuan, TY-U; Jinyuan, JY-U; Xiaodian, XD-U) and a suburban site (Shanglan, SL-B) in Taiyuan during a high O3 period (from July 20 to August 3, 2020). The average mixing ratio of HCHO at XD-U (8.1 ± 2.8 ppbv) was comparable to those at TY-U (7.4 ± 2.1 ppbv) and JY-U (7.0 ± 2.3 ppbv) but higher (p < 0.01) than that at SL-B (4.9 ± 2.3 ppbv). HCHO contributed to 54.3–59.9 % of the total ozone formation potentials (OFPs) of non-methane hydrocarbons (NMHCs) at four sites. The diurnal variation of HCHO concentrations reached a peak value at 12:00–15:00, which may be attributed to the strong photochemical reaction. To obtain more accurate source results of HCHO under the condition of photochemical loss, the initial concentrations of NMHCs were estimated based on photochemical age parameterization and incorporated into the positive matrix factorization (PMF) model (termed IC-PMF). According to the IC-PMF results, secondary formation (SF) contributed the most to HCHO at XD-U (35.6 %) and SL-B (25.1 %), whereas solvent usage (SU) (40.9 %) and coking sources (CS) (36.0 %) were the major sources at TY-U and JY-U, respectively. Compared to the IC-PMF, the conventional PMF analysis based on the observed data underestimated the contributions of SU (100.5–154.2 %) and biogenic sources (BS) (28.5–324.7 %). Further reapportionment of secondary HCHO by multiple linear regression indicated that SU dominated the sources of HCHO at SL-B (28.3 %) and TY-U (41.7 %), while industrial emissions (IE) and CS contributed the most to XD-U (26.6 %) and JY-U (43.0 %) in Taiyuan from north to south, respectively.

Investigation of O3-precursor relationship nearby oil fields of Shandong, China

Oil exploitation can release a large amount of volatile organic compounds (VOCs), which play an important role in tropospheric chemistry and contribute to ozone (O3) and secondary organic aerosols (SOA) formation in its surrounding environment. To evaluate the impact of oil exploitation on tropospheric O3 formation, a comprehensive field campaign on O3 and its precursors (VOC, NOx, etc) was conducted during May–September 2019 in a site nearby oil fields of Shandong province, China. The average mixing ratio of the total VOC (TVOC) was 59.2 ± 30.2 ppbv, and alkanes contributed 78% of TVOC (with C2–C5 alkanes as the main contributors). A 0-D box model incorporating the latest Master Chemical Mechanism (MCMv3.3.1) was applied using observations as constraints, and we found that the O3 formation was mainly under transitional and VOC-limited regime for high-O3 and low-O3 periods, respectively. The relative incremental reactivity (RIR) values from individual AVOC species were basically consistent with those calculated from OH reactivity, and both metrics suggested that C3–C5 alkanes, C2–C5 alkenes, and C7–C9 aromatics were the most sensitive VOC species to O3 formation. The results from empirical kinetic modeling approach (EKMA) indicated large day-to-day variations of photochemical regimes, which covered VOC-limited, transitional, and NOx-limited regimes on a daily basis during the five-month campaign. The emission reduction modeling with a large number of scenarios further suggested that the reduction of anthropogenic VOC and NOx at a ratio of 1:3 would be a more practical strategy for mitigation of the local O3 pollution. These results could provide a basis for understanding the O3-precursor relationship nearby the oil field area, and the derived policy-relevant emission control strategy could provide guidance for other oil field in Shandong and other regions to take effective O3 control measures.

Characteristics and Health Risk Assessment of BTESX in the Northern Suburbs of Nanjing

AMA GC5000BTX was used to monitor the mixing ratio of benzene, toluene, ethylbenzene, m,p-xylene, o-xylene, and styrene (BTESX) in the atmosphere of the northern suburb of Nanjing from January 2014 to December 2016. The temporal variation characteristics of BTESX and the influence of meteorological elements on it were analyzed, and the characteristic ratio method (T/B) was used to qualitatively analyze the source of BTESX. Finally, the human exposure analysis and evaluation method of EPA was used to evaluate the health risk of BTESX. The results showed that during the observation period, the average mixing ratio of BTESX was (7.28±6.63)×10-9, and the mixing ratio of benzene was the highest at (2.45±3.91)×10-9. The mixing ratio of other species from large to small was toluene>ethylbenzene>m,p-xylene>o-xylene>styrene, which were (2.41±2.61)×10-9, (1.37±1.28)×10-9, (0.51±0.48)×10-9, (0.3±0.36)×10-9, and (0.22±0.42)×10-9, respectively. Due to the existence of stable aromatic sources, the monthly and seasonal variation in BTESX mixing ratio was not as obvious as that of other species (NOx, CO, SO2, PM2.5, etc.). The weekend effect of BTESX and other pollutants was not significant. The mixing ratio of BTESX was largely affected by the short distance transportation of chemical enterprises and traffic trunk roads in the northeast, resulting in a large mixing ratio of BTESX in the northeast. The mixing ratio of BTESX was jointly affected by relative humidity and temperature, and its high value area was mainly located in the range of 30%-70% relative humidity. In this range of relative humidity, the high value range of BTESX volume fraction increased with the elevation of temperature. The HI (hazard index) of BTESX in different seasons was within the safety range recognized by EPA, whereas the R (carcinogenic risk of benzene) value was higher than the safety threshold specified by EPA. At the same time, the HI and R values were higher in summer, to which great attention should be paid.