Formation Of Secondary Pollutants Research Articles

Synthesis of magnetic layered double hydroxide (Fe3O4@CuCr-LDH) decorated with ZIF-8 for efficient sonocatalytic degradation of tetracycline

A series of Fe3O4@CuCr-LDH hybrids decorated with different amount of ZIF-8 (FLZ, 10–40 wt%) was prepared using simple methods and characterized with different techniques. The activity of the synthesized nanocomposites was investigated in the sonocatalytic degradation of tetracycline (TC) antibiotic from wastewater. When the content of ZIF-8 in the nanocomposite structure was 20 wt%, the FLZ-20 sonocatalyst exhibited the high performance in the sonocatalytic removal of TC. At optimum conditions (0.7 g/L catalyst dosage, pH of 7, 50 mg/L initial concentration of antibiotic, and 15 min sonication time) of the sonocatalytic removal of TC approached to 91.4% under ultrasonic irradiation (USI) using FLZ-20. This efficiency was much higher than those of obtained results by Fe3O4@CuCr-LDH and pristine ZIF-8. The formed ●OH and ●O2− exhibited the major roles in the sonocatalytic TC degradation process. The excellent performance of FLZ-20 can be attributed to the heterojunctions created between composite components, which could improve the electron transfer ability and effectively separate e−/h+ pairs. In addition, FLZ-20 showed the superior reusability and stability during three successive recycling. Moreover, the facile magnetically separation of the sonocatalyst from the aqueous solution was another outstanding feature, which prevents the formation of secondary pollutants. It can be concluded that the fabrication of heterojunctions is an efficient procedure to promote the sonocatalytic acting of the catalyst.

Air quality and public health effects of dairy digesters in California

The dairy industry in California emits large amounts of methane (CH4) that contributes significantly to the state's overall Greenhouse Gas (GHG) budget. Reducing CH4 emissions has become a key priority for dairy farms in support of California's GHG reduction goals. Anaerobic digesters designed to capture CH4 from animal manure present a practical option for reducing CH4 emissions, but a comprehensive evaluation of the local air quality impacts of this technology has not been previously undertaken. The simplest digester configurations decrease local emissions of volatile organic compounds (VOCs) but increase emissions of oxides of nitrogen (NOx), potentially changing local air quality. Here, we evaluate the air quality implications of widespread digester adoption in the year 2050 across the San Joaquin Valley (SJV) in central California, which is home to the highest concentration of dairy farms in the state. Changes to concentrations of air pollutants including ozone (O3), airborne particulate matter with diameter smaller than 2.5 μm (PM2.5), and various PM2.5 chemical components are predicted using the UCD/CIT chemical transport model at 4 km resolution. Dairy digester adoption is evaluated within two regional energy scenarios, including a business as usual (BAU) scenario and an 80% greenhouse gas reduction (GHGAi) scenario, to consider potential changes to the chemical regime that governs formation of secondary air pollution. Concentrations are evaluated across 32 randomly selected weeks over a 10-year period from the year 2046–2055 to establish a long-term average impact in the presence of El Niño Southern Oscillation (ENSO) variability. Regional weather patterns are downscaled from Global Climate Model simulations under the RCP8.5 global scenario. The results indicate that baseline dairy emissions make minor contributions to air pollutant concentrations in 2050. Under a worst-case scenario for digester adoption, PM2.5 concentrations would increase by 0.06 μg/m3 (current standard = 9 μg/m3), and maximum daily 8-h average (MDA8) O3 would change by −1.0 ppb to +0.2 ppb depending on the surrounding regional energy scenario (current standard = 70 ppb). A health impact analysis shows that the widespread use of dairy digesters would result in fewer than 0.1 additional deaths per 100,000 people due to changing air pollution. For comparison, this level of mortality change is more than 100 times smaller than the risk posed by seasonal flu. Further, Environmental Justice analysis indicates that the implementation of digesters will not influence the exposure disparities among different racial groups in either the SJV or the surrounding San Francisco Bay & Sacramento area. These findings suggest that dairy digesters can be widely adopted in central California to reduce GHG emissions with minimal effect on regional air quality and public health.

Pretreatment of wastepaper with an aqueous solution of amino acid-derived ionic liquid for biochar production as adsorbent

The carbonization of lignocellulosic biomass with ionic liquids (ILs) are considered as an advantageous approach for the preparation of carbonaceous materials. The commonly used imidazolium and pyridinium based ILs have drawbacks such as toxicity, resistance to biodegradation, high cost and viscosity. These issues can be mitigated by diluting ILs with water, although excessive water content above 1 wt% can reduce the solubility of biomass. This research aims to investigate the potential of pretreating wastepaper with a “fully green” ILs, amino acid-based IL with high water content, followed by pyrolysis without IL, in enhancing the properties of biochar. For this purpose, the paper was treated with an aqueous solution of IL cysteine nitrate ([Cys][NO3]), and the IL was not involved in the pyrolysis process to prevent the formation of secondary gaseous pollutants. The findings revealed that the hemicellulose and mineral filler in the paper were eliminated during pretreatment, leading to higher carbon content but lower oxygen content. As a result, the biochar exhibited micropores of 0.42 cm3g-1 and a specific surface area of 1011.21 m2 g−1. The biochar demonstrated high adsorption capacities for Cd2+, enrofloxacin, bisphenol A, ciprofloxacin, and tetracycline, with values of 45.20 mg g−1, 49.82 mg g−1, 49.90 mg g−1, 49.88 mg g−1, and 49.65 mg g−1, respectively. The proposed mechanism for the adsorption of enrofloxacin by the biochar primarily involves physical adsorption such as pore filling and electrostatic interactions, along with chemical adsorption facilitated by graphitic nitrogen.

Potential Estimation of Secondary Pollutant Formation of BVOC from Peltophorum pterocarpum in Urban Area

Cimate change affects the emission of biogenic volatile organic compounds (BVOCs) from plants, especially isoprene, α-pinene, and β-pinene. These compounds play vital role in the secondary organic aerosol potential (SOAP) and ozone formation potential (OFP) through photochemical reactions. In Thailand, daytime temperatures typically reach up to 40°C resulting in potential plant stress. The considered plant Peltophorum pterocarpum, emits high levels of BVOCs and is widely cultivated in the urban areas of Bangkok. Consequently, this research aimed to study the variations in BVOC concentration, SOAP, and OFP associated with Peltophorum pterocarpum, during the daytime. The BVOCs (isoprene, α – pinene, and β – pinene) were sampled using a dynamic enclosure system from 9:00 to 11:00 local time and analyzed using gas chromatography with a flame ionization detector. SOAP and OFP were estimated using fractional aerosol coefficient and maximum incremental reactivity. The results revealed an average BVOC concentration of 4.68 μg/m3, which depended on temperature and light intensity. The highest SOAP and OFP were 1,367.10 and 188.58 μg/m3, respectively, which were largely influenced by β – piene. This study aids in understanding the role of secondary pollutant formation involving BVOCs emitted from trees in urban areas, which can lead to the selection of low BVOC-emitting tree species and improvement of guidelines for planning urban forest areas.

Missing Measurements of Sesquiterpene Ozonolysis Rates and Composition Limit Understanding of Atmospheric Reactivity.

Emissions of biogenic reactive carbon significantly influence atmospheric chemistry, contributing to the formation and destruction of secondary pollutants, such as secondary organic aerosol and ozone. While isoprene and monoterpenes are a major fraction of emissions and have been extensively studied, substantially less is known about the atmospheric impacts of higher-molecular-weight terpenes such as sesquiterpenes. In particular, sesquiterpenes have been proposed to play a significant role in ozone chemical loss due to the very high ozone reaction rates of certain isomers. However, relatively little data are available on the isomer-resolved composition of this compound class or its role in ozone chemistry. This study examines the chemical diversity of sesquiterpenes and availability of ozone reaction rate constants to evaluate the current understanding of their ozone reactivity. Sesquiterpenes are found to be highly diverse, with 72 different isomers reported and relatively few isomers that contribute a large mass fraction across all studies. For the small number of isomers with known ozone reaction rates, estimated rates may be 25 times higher or lower than measurements, indicating that estimated reaction rates are highly uncertain. Isomers with known ozone reaction rates make up approximately half of the mass of sesquiterpenes in concentration and emission measurements. Consequently, the current state of the knowledge suggests that the total ozone reactivity of sesquiterpenes cannot be quantified without very high uncertainty, even if isomer-resolved composition is known. These results are in contrast to monoterpenes, which are less diverse and for which ozone reaction rates are well-known, and in contrast to hydroxyl reactivity of monoterpenes and sesquiterpenes, for which reaction rates can be reasonably well estimated. Improved measurements of a relatively small number of sesquiterpene isomers would reduce uncertainties and improve our understanding of their role in regional and global ozone chemistry.

A Review of Ultrasonic Treatment in Mineral Flotation: Mechanism and Recent Development.

Ultrasonic treatment has been widely used in the mineral flotation process due to its advantages in terms of operational simplicity, no secondary pollutant formation, and safety. Currently, many studies have reported the effect of ultrasonic treatment on mineral flotation and shown excellent flotation performance. In this review, the ultrasonic mechanisms are classified into three types: the transient cavitation effect, stable cavitation effect, and acoustic radiation force effect. The effect of the main ultrasonic parameters, including ultrasonic power and ultrasonic frequency, on mineral flotation are discussed. This review highlights the uses of the application of ultrasonic treatment in minerals (such as the cleaning effect, ultrasonic corrosion, and desulfuration), flotation agents (such as dispersion and emulsification and change in properties and microstructure of pharmaceutical solution), and slurry (such formation of microbubbles and coalescence). Additionally, this review discusses the challenges and prospects of using ultrasonic approaches for mineral flotation. The findings demonstrate that the application of the ultrasonic effect yields diverse impacts on flotation, thereby enabling the regulation of flotation behavior through various treatment methods to enhance flotation indices and achieve the desired objectives.

Underestimated contribution of open biomass burning to terpenoid emissions revealed by a novel hourly dynamic inventory

Terpenoids play a crucial role in atmospheric chemistry, contributing significantly to the formation of ozone and secondary organic aerosol. However, the accurate quantification of terpenoid emissions from biomass burning is currently lacking, leading to underestimated air quality impacts. This study developed a near real-time hourly open biomass burning (OBB) emission inventory named OBEIC, which incorporated geostationary and polar-orbiting satellite fire radiative power. The OBEIC inventory provided emission estimates of 69 terpenoids, categorized into four groups, at an hourly resolution. Monoterpenes were the dominant contributors to the total emissions, accounting for 58 % of the total terpenoid emissions from OBB. Notably, only 24 % of the total monoterpenes emitted from OBB were accounted for by α-pinene and β-pinene, indicating the importance of quantifying emissions of other monoterpene species such as limonene and camphene. Additionally, oxygenated terpenoids, which were previously overlooked, contribute to 20 % of total terpenoid emissions from OBB. Diurnally, the emissions of terpenoids were primarily concentrated during the daytime (61 %); however, this study revealed the significance of nighttime emissions (39 %) as well. When compared to the biogenic and anthropogenic emissions, OBB made substantial contributions to nighttime isoprene (99.8 %), monoterpene (66.8 %), and sesquiterpene (61.7 %) emissions where OBB occurs (in 3 km range), suggesting its significant role in nighttime secondary pollutant formation. The methodology developed in this study has the potential to reduce uncertainties in OBB emissions estimation.

Response of protonated, adduct, and fragmented ions in Vocus proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS)

Abstract. Volatile organic compounds (VOCs) affect secondary pollutant formation via active chemistry. Proton-transfer-reaction mass spectrometry (PTR-MS) is one of the most important techniques to study the highly variable spatial and temporal characteristics of VOCs. The response of protonated, adduct, and fragmented ions in PTR-MS in changing instrument settings and varying relative humidity (RH) requires rigorous characterization. Herein, we present dedicatedly designed laboratory experiments conducted to investigate the response of these ions for 21 VOCs, including 12 oxygenated VOCs and 2 nitriles, using the recently developed Vocus PTR-MS. Our results show that the focusing ion–molecule reactor (FIMR) axial voltage increases sensitivity by 3 to 4 orders of magnitude but does not significantly change the fractions of protonated ions. Reducing the FIMR pressure, however, substantially increases fragmentation. Applying a high radio frequency (RF) amplitude radially to the FIMR can enhance sensitivity by 1 to 2 orders of magnitude without affecting the protonated ion fractions. The change in big segmented quadrupole (BSQ) amplitude mainly affects sensitivity and protonated ion fraction by modifying ion transmission. The relationship between sensitivity and proton-transfer reaction rate constant is complicated by the influences from both ion transmission and protonated ion fraction. The protonated ions of most VOCs studied (19 out of 21) show less than 15 % variations in sensitivity as RH increases from ∼ 5% to ∼ 85 %, except for some long-chain aldehydes which show a positive RH variation of up to 30 %. Our results suggest that the Vocus PTR-MS can reliably quantify the majority of VOCs under ambient conditions with varying RH. However, caution is advised for small oxygenates such as formaldehyde and methanol due to their low sensitivity and for long-chain aldehydes due to their slight RH dependence and fragmentation.

Revealing the Contribution of Interfacial Processes to Atmospheric Oxidizing Capacity in Haze Chemistry.

The atmospheric oxidizing capacity is the most important driving force for the chemical transformation of pollutants in the atmosphere. Traditionally, the atmospheric oxidizing capacity mainly depends on the concentration of O3 and other gaseous oxidants. However, the atmospheric oxidizing capacity based on gas-phase oxidation cannot accurately describe the explosive growth of secondary particulate matter under complex air pollution. From the chemical perspective, the atmospheric oxidizing capacity mainly comes from the activation of O2, which can be achieved in both gas-phase and interfacial processes. In the heterogeneous or multiphase formation pathways of secondary particulate matter, the enhancement of oxidizing capacity ascribed to the O2/H2O-involved interfacial oxidation and hydrolysis processes is an unrecognized source of atmospheric oxidizing capacity. Revealing the enhanced oxidizing capacity due to interfacial processes in high-concentration particulate matter environments and its contribution to the formation of secondary pollution are critical in understanding haze chemistry. The accurate evaluation of atmospheric oxidizing capacity ascribed to interfacial processes is also an important scientific basis for the implementation of PM2.5 and O3 collaborative control in China and around the world.

Nocturnal ozone enhancement in Shandong Province, China, in 2020–2022: Spatiotemporal distribution and formation mechanisms

Nighttime ozone enhancement (NOE) can increase the oxidation capacity of the atmosphere by stimulating nitrate radical formation and subsequently facilitating the formation of secondary pollutants, thereby affecting air quality in the following days. Previous studies have demonstrated that when nocturnal ozone (O3) concentrations exceed 80 μg/m3, it leads to water loss and reduction of plant yields. In this study, the characteristics and mechanisms of NOE over Shandong Province as well as its 16 cities were analyzed based on observed hourly O3 concentrations from 2020 to 2022. The analysis results show that NOE predominantly occurred in the periods of 0:00–3:00 (41 %). The annual mean frequency of NOE events was ~64 days/year, approximately 4–7 days per month. The average concentration of nocturnal O3 peak (NOP) was ~72.6 μg/m3. Notably, high NOP was observed in the period from April to September with the maximum in June. Coastal cities experienced more NOE events. Typical NOE events characterized by high NOP concentrations in the coastal cities of QingDao, WeiHai and YanTai in June 2021 were selected for detailed analysis with a regional chemical transport model. The results showed that high levels of O3 in eastern coastal cities during NOE events primarily originate from horizontal transport over the sea, followed by vertical transport. During the daytime, O3 and its precursors are transported to the Yellow Sea by westerly winds, leading to the accumulation of O3 near the sea and coastline. Consequently, under the influence of prevailing winds, the movement of O3 pollution belts from the sea to land causes rapid increases in near-surface O3 levels. Meanwhile, vertical transport can also contribute to NOE in coastal areas. The high-level O3 in the upper atmosphere generally originates from long-distance transport and turbulent transport of O3 produced near the ground during the daytime. At night, the absence of chemicals that consume O3 in the upper air and descending air flow carries O3 to the near-surface. The impacts of other O3-depletion processes (such as dry deposition) on NOE are less pronounced than those of transport processes.

Additional HONO and OH Generation from Photoexcited Phenyl Organic Nitrates in the Photoreaction of Aromatics and NOx.

HONO acts as a major OH source, playing a vital role in secondary pollutant formation to deteriorate regional air quality. Strong unknown sources of daytime HONO have been widely reported, which significantly limit our understanding of radical cycling and atmospheric oxidation capacity. Here, we identify a potential daytime HONO and OH source originating from photoexcited phenyl organic nitrates formed during the photoreaction of aromatics and NOx. Significant HONO (1.56-4.52 ppb) and OH production is observed during the photoreaction of different kinds of aromatics with NOx (18.1-242.3 ppb). We propose an additional mechanism involving photoexcited phenyl organic nitrates (RONO2) reacting with water vapor to account for the higher levels of measured HONO and OH than the model prediction. The proposed HONO formation mechanism was evidenced directly by photolysis experiments using typical RONO2 under UV irradiation conditions, during which HONO formation was enhanced by relative humidity. The 0-D box model incorporated in this mechanism accurately reproduced the evolution of HONO and aromatic. The proposed mechanism contributes 5.9-36.6% of HONO formation as the NOx concentration increased in the photoreaction of aromatics and NOx. Our study implies that photoexcited phenyl organic nitrates are an important source of atmospheric HONO and OH that contributes significantly to atmospheric oxidation capacity.

Impacts of Anthropogenic Emission Reduction on Urban Atmospheric Oxidizing Capacity During the COVID-19 Lockdown

In recent years， regional compound air pollution events caused by fine particles （PM2.5） and ozone （O3） have occurred frequently in economically developed areas of China， in which atmospheric oxidizing capacity （AOC） has played an important role. In this study， the WRF-CMAQ model was used to study the impacts of anthropogenic emission reduction on AOC during the COVID-19 lockdown period. Three representative cities in eastern China （Shijiazhuang， Nanjing， and Guangzhou） were selected for an in-depth analysis to quantify the contribution of meteorology and emissions to the changes in AOC and oxidants and to discuss the impact of AOC changes on the formation of secondary pollutants. The results showed that， compared with that in the same period in 2019， the urban average AOC in Shijiazhuang， Nanjing， and Guangzhou in 2020 increased by 60%， 48.7%， and 12.6%， respectively. The concentrations of O3， hydroxyl radical （·OH）， and nitrogen trioxide （NO3·） increased by 1.6%-26.4%， 14.8%-73.3%， and 37.9%-180%， respectively. The AOC in the three cities increased by 0.06×10-4， 0.12×10-4， and 0.33×10-4 min-1， respectively， due to emission reduction. The meteorological change increased AOC in Shijiazhuang and Nanjing by 20% and 17.9%， respectively， but decreased AOC in Guangzhou by -9.3%. Enhanced AOC led to an increase in the nitrogen oxidation ratio （NOR） and VOCs oxidation ratio （VOR） and promoted the transformation of primary pollutants to secondary pollutants. This offset the effects of primary emission reduction and resulted in a nonlinear decline in secondary pollutants compared to emissions during the COVID-19 lockdown.

Parameterizations of US wildfire and prescribed fire emission ratios and emission factors based on FIREX-AQ aircraft measurements

Abstract. Extensive airborne measurements of non-methane organic gases (NMOGs), methane, nitrogen oxides, reduced nitrogen species, and aerosol emissions from US wild and prescribed fires were conducted during the 2019 NOAA/NASA Fire Influence on Regional to Global Environments and Air Quality campaign (FIREX-AQ). Here, we report the atmospheric enhancement ratios (ERs) and inferred emission factors (EFs) for compounds measured on board the NASA DC-8 research aircraft for nine wildfires and one prescribed fire, which encompass a range of vegetation types. We use photochemical proxies to identify young smoke and reduce the effects of chemical degradation on our emissions calculations. ERs and EFs calculated from FIREX-AQ observations agree within a factor of 2, with values reported from previous laboratory and field studies for more than 80 % of the carbon- and nitrogen-containing species. Wildfire emissions are parameterized based on correlations of the sum of NMOGs with reactive nitrogen oxides (NOy) to modified combustion efficiency (MCE) as well as other chemical signatures indicative of flaming/smoldering combustion, including carbon monoxide (CO), nitrogen dioxide (NO2), and black carbon aerosol. The sum of primary NMOG EFs correlates to MCE with an R2 of 0.68 and a slope of −296 ± 51 g kg−1, consistent with previous studies. The sum of the NMOG mixing ratios correlates well with CO with an R2 of 0.98 and a slope of 137 ± 4 ppbv of NMOGs per parts per million by volume (ppmv) of CO, demonstrating that primary NMOG emissions can be estimated from CO. Individual nitrogen-containing species correlate better with NO2, NOy, and black carbon than with CO. More than half of the NOy in fresh plumes is NO2 with an R2 of 0.95 and a ratio of NO2 to NOy of 0.55 ± 0.05 ppbv ppbv−1, highlighting that fast photochemistry had already occurred in the sampled fire plumes. The ratio of NOy to the sum of NMOGs follows trends observed in laboratory experiments and increases exponentially with MCE, due to increased emission of key nitrogen species and reduced emission of NMOGs at higher MCE during flaming combustion. These parameterizations will provide more accurate boundary conditions for modeling and satellite studies of fire plume chemistry and evolution to predict the downwind formation of secondary pollutants, including ozone and secondary organic aerosol.

Tree species classification improves the estimation of BVOCs from urban greenspace

Accurate estimation of biogenic volatile organic compounds (BVOCs) emissions from urban plants is important as BVOCs affect the formation of secondary pollutants and human health. However, uncertainties exist for the estimation of BVOCs emissions from urban greenspace due to the lack of tree species classification with high spatial resolution. Here, we generated a tree species classification dataset with 10 m resolution to estimate tree species-level BVOCs emissions and quantify their impact on air quality in Shenzhen in southern China. The results showed that for the entire city, the BVOCs emissions based on traditional plant functional types (PFTs) dataset were substantially underestimated compared with the tree species classification data (6.37 kt versus 8.23 kt, with 22.60 % difference). The underestimation is particularly prominent in urban built-up areas, where our estimation was 1.65 kt, nearly twice of that based on PFTs data (0.86 kt). BVOCs estimation in built-up areas contributed approximately 20.07 % to the total. These BVOCs contributed substantially to the increase of ambient O3, but had limited impacts to ambient fine particulate matter (PM2.5). Our results underscore the importance of high spatial resolution tree species-level classification in more accurate estimation of BVOCs, especially in highly developed urban areas. The enhanced understanding of the patterns of BVOCs emissions by urban trees and the impact on secondary pollutants can better support fine-scale tree planning and management for livable environments in urban areas.

Atmospheric HONO emissions in China: Unraveling the spatiotemporal patterns and their key influencing factors

Nitrous acid (HONO) can be photolyzed to produce hydroxyl radicals (OH) in the atmosphere. OH plays a critical role in the formation of secondary pollutants like ozone (O3) and secondary organic aerosols (SOA) via various oxidation reactions. Despite the abundance of recent HONO studies, research on national HONO emissions in China remains relatively limited. Therefore, this study employed a "wetting-drying" model and bottom-up approach to develop a high-resolution gridded inventory of HONO emissions for mainland China using multiple data. We used the Monte Carlo method to estimate the uncertainty in HONO emissions. In addition, the primary sources of HONO emissions were identified and their spatiotemporal distribution and main influencing factors were studied. The results indicated that the total HONO emissions in mainland China in 2016 were 0.77 Tg N (R50: 0.28–1.42 Tg N), with soil (0.42 Tg N) and fertilization (0.26 Tg N) as the primary sources, jointly contributing to over 87% of the total. Notably, the North China Plain (NCP) had the highest HONO emission density (3.51 kg N/ha/yr). Seasonal HONO emissions followed the order: summer (0.38 kg N/ha) > spring (0.19 kg N/ha) > autumn (0.17 kg N/ha) > winter (0.06 kg N/ha). Moreover, HONO emissions were strongly correlated with fertilization, cropland, temperature, and precipitation. This study provides vital scientific groundwork for the atmospheric nitrogen cycle and the formation of secondary pollutants.

Characteristics of air pollution complex in a typical chemical industrial development zone in eastern China

VOCs (volatile organic compounds) have an important impact on the atmospheric environment, climate and human health. In a typical chemical industrial development zone in eastern China, 123 kinds of VOCs were on-line monitored simultaneously at three sites using the GC-FID/MS system for one year. The seasonal and diurnal variations of composition and concentration of VOCs were compared and analyzed systematically. The VOCs features existed significant differences at the three sites, which were greatly affected by the types and emissions of surrounding enterprises. The alkanes appeared as the major pollutants at the site adjacent to petrochemical processing enterprises (site A), while OVOCs were the majority at the other two sites, which were around by the fine chemical enterprises (site B and C). The TVOC concentrations presented seasonal differences at the three sites, which showed higher values in summer (468.6 μg/m3) at site A, in winter (409.2 μg/m3) at site B，and in autumn (298.9 μg/m3) at site C, respectively. The isopentane (16.8%) and ethylene oxide (17.9%) made up the largest proportion of the VOCs at site A and B, respectively. While it was more susceptible to the effects of dichloromethane, 1,2-dichloroethane and chloromethane at site C. Three pollution events of ethylene oxide, isopentane and dichloromethane were analyzed and traced based on the prevailing wind and the change of concentration at the three sites. Further analysis of the impact of VOCs on the formation of secondary pollutants of O3 and PM2.5 found that the contribution of local O3 (28.1 %) in summer was significantly larger in the study area than that in non-industrial area. The multiphase chemical reactions were more likely to occur in autumn, which promoted the formation of secondary PM2.5, showing the correlation coefficient of 0.73 between the secondary organic aerosol formation potential of VOCs and PM2.5.

Atmospheric impact of 2-methylpentanal emissions: kinetics, photochemistry, and formation of secondary pollutants

Abstract. The tropospheric fate of 2-methylpentanal (2MP) has been investigated in this work. First, the photochemistry of 2MP under simulated solar conditions was investigated by determining the UV absorption cross sections (220–360 nm) and the effective photolysis quantum yield in the UV solar actinic region (λ > 290 nm). The photolysis rate coefficient in that region was estimated using a radiative transfer model. Photolysis products were identified by Fourier transform infrared (FTIR) spectroscopy. Secondly, a kinetic study of the chlorine (Cl) and hydroxyl (OH) reactions of 2MP was also performed at 298 K and as a function of temperature (263–353 K), respectively. For the Cl reaction, a relative kinetic method was used in a smog chamber coupled to FTIR spectroscopy, whereas for the OH reaction, the pulsed laser photolysis (PLP) with laser-induced fluorescence (LIF) technique was employed. The estimated lifetime of 2MP depends on the location, the season, and the time of the day. Under mild–strong irradiation conditions, UV photolysis of 2MP may compete with its OH reaction in a mid-latitude inland urban atmosphere, while Cl reaction dominates in mid-latitude coastal urban areas at dawn. Finally, the gaseous product distribution of the Cl and OH reactions was measured in a smog chamber as well as the formation of secondary organic aerosols (SOAs) in the Cl reaction and its size distribution (diameter between 5.6 and 560 nm). The implications for air quality are discussed based on the observed products.

The atmospheric oxidizing capacity in China – Part 1: Roles of different photochemical processes

Abstract. Atmospheric oxidation capacity (AOC) characterizes the ability of the atmosphere to scavenge air pollutants. However, the processes involved in China, where anthropogenic emissions have changed dramatically in the past decade, are not fully understood. A detailed analysis of different parameters that determine the AOC in China is presented on the basis of numerical simulations performed with the regional chemical–meteorological Weather Research and Forecasting model with Chemistry (WRF-Chem). The model shows that the aerosol effects related to extinction and heterogeneous processes produce a decrease in surface ozone of approximately 8–10 ppbv in NOx-limited rural areas and an increase of 5–10 ppbv in VOC-limited urban areas. In this latter case, the ozone increase is noticeable for aerosol concentrations ranging from 20 to 45 µg m−3 in July 2018. The ozone reduction in NOx-sensitive regions is due to the combined effect of nitrogen dioxide and peroxy radical uptake on particles and of the light extinction by aerosols, which affects the photodissociation rates. The ozone increase in VOC-sensitive areas is attributed to the uptake of NO2 by aerosols, which is offset by the reduced ozone formation associated with HO2 uptake and with aerosol extinction. Our study concludes that more than 90 % of the daytime AOC is due to the reaction of the hydroxyl radical with VOCs and carbon monoxide. In urban areas, during summertime, the main contributions to daytime AOC are the reactions of OH with alkene (30 %–50 %), oxidized volatile organic compounds (OVOCs) (33 %–45 %), and carbon monoxide (20 %–45 %). In rural areas, the largest contribution results from the reaction of OH with alkenes (60 %). Nocturnal AOC is dominantly attributed to the reactions with the nitrate radical (50 %–70 %). Our results shed light on the contribution of aerosol-related NOx loss and the high reactivity of alkenes for photochemical pollution. With the reduction in aerosols and anthropogenic ozone precursors, the chemistry of nitrogen and temperature-sensitive VOCs will become increasingly important. More attention needs to be paid to the role of photodegradable OVOCs and nocturnal oxidants in the formation of secondary pollutants.

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.

Measurements of volatile organic compounds in ambient air by gas-chromatography and real-time Vocus PTR-TOF-MS: calibrations, instrument background corrections, and introducing a PTR Data Toolkit

Abstract. Volatile organic compound (VOC) emissions and subsequent oxidation contribute to the formation of secondary pollutants and poor air quality in general. As more VOCs at lower mixing ratios have become the target of air quality investigations, their quantification has been aided by technological advancements in proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS). However, such quantification requires appropriate instrument background measurements and calibrations, particularly for VOCs without calibration standards. This study utilized a Vocus PTR-TOF-MS coupled with a gas chromatograph for real-time and speciated measurements of ambient VOCs in Boulder, Colorado, during spring 2021. The aim of these measurements was to understand and characterize instrument response and temporal variability as to inform the quantification of a broader range of detected VOCs. Fast, frequent calibrations were made every 2 h in addition to daily multipoint calibrations. Sensitivities derived from the fast calibrations were 5 ± 6 % (average and 1 standard deviation) lower than those derived from the multipoint calibrations due to an offset between the calibrations and instrument background measurement. This offset was caused, in part, by incomplete mixing of the standard with diluent. These fast calibrations were used in place of a normalization correction to account for variability in instrument response and accounted for non-constant reactor conditions caused by a gradual obstruction of the sample inlet. One symptom of these non-constant conditions was a trend in fragmentation, although the greatest observed variability was 6 % (1 relative standard deviation) for isoprene. A PTR Data Toolkit (PTR-DT) was developed to assess instrument performance and rapidly estimate the sensitivities of VOCs which could not be directly calibrated on the timescale of the fast calibrations using the measured sensitivities of standards, molecular properties, and simple reaction kinetics. Through this toolkit, the standards' sensitivities were recreated within 1 ± 8 % of the measured values. Three clean-air sources were compared: a hydrocarbon trap, zero-grade air and ultra-high purity nitrogen, and a catalytic zero-air generator. The catalytic zero-air generator yielded the lowest instrument background signals for the majority of ions, followed by the hydrocarbon trap. Depending on the ionization efficiency, product ion fragmentation, ion transmission, and instrument background, standards' limits of detection (5 s measurement integration) derived from the catalytic zero-air generator and the fast calibration sensitivities ranged from 2 ppbv (methanol) to 1 pptv (decamethylcyclopentasiloxane; D5 siloxane) with most standards having detection limits below 20 pptv. Finally, applications of measurements with low detection limits are considered for a few low-signal species including sub-parts-per-trillion by volume (pptv) enhancements of icosanal (and isomers; 1 min average) in a plume of cooking emissions, and sub-parts-per-trillion by volume enhancements in dimethyl disulfide in plumes containing other organosulfur compounds. Additionally, chromatograms of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane (D3, D4, and D5 siloxanes, respectively), combined with high sensitivity, suggest that online measurements can reasonably be associated with the individual isomers.