Photochemical Assessment Monitoring Stations Research Articles

Assessment of VOCs emission inventory in Seoul through spatiotemporal observations using passive and online PAMS measurements

We have conducted a quantitative analysis of volatile organic compounds (VOCs) in Seoul from September 2022 to June 2023, employing passive air samplers (PAS) at 25 sites and continuous monitoring at five photochemical assessment monitoring stations (PAMS). Comparing VOCs concentrations and compositions from PAS and PAMS during the same time periods, we found that most VOCs showed no significant difference (p-value >0.05) between the methods, except for olefins, which were overestimated by 24 % in passive sampling, confirming PAS as an effective tool for assessing the spatial distribution of VOCs species over large areas. Throughout Seoul, median values of total volatile organic compounds (TVOCs) concentrations collected with passive samplers remained stable with a standard deviation of 1.22 ppbv, typically ranging from 11 to 13 ppbv, except for an increase during winter in the southwestern regions of the city, where intense industrial and vehicular emissions are reported in the current Clean Air Policy Support System (CAPSS) emissions inventory. Positive matrix factorization (PMF) analysis using the passive data revealed general consistency in the spatial distribution of area and road emissions when compared with CAPSS emission inventory, although localized discrepancies were observed. In quantitative assessments of TVOCs comparing PAS observations with emission-based models, modeled values were within 1.5 times the interquartile range of observed PAS concentrations over Seoul. However, the lack of detection of emission hotspots in southeastern Seoul in the PAS data, coupled with the omission of photochemical loss in our dispersion-only models, indicates that the current CAPSS emission inventory may significantly underestimate actual ambient VOCs levels, especially in summer.

Evaluation of Aeris mid-infrared absorption (MIRA), Picarro CRDS (cavity ring-down spectroscopy) G2307, and dinitrophenylhydrazine (DNPH)-based sampling for long-term formaldehyde monitoring efforts

Abstract. Current formaldehyde (HCHO) measurement networks rely on the TO-11A offline chemical derivatization technique, which can be resource intensive and limited in temporal resolution. In this work, we evaluate the field performance of three new commercial instruments for continuous in situ formaldehyde monitoring: the Picarro cavity ring-down spectroscopy G2307 gas concentration analyzer and Aeris Technologies' mid-infrared absorption Pico and Ultra gas analyzers. All instruments require regular drift correction, which is accomplished through instrument zeroing using dinitrophenylhydrazine (DNPH)-coated cartridges, Drierite, or molecular sieves, while heated Hopcalite failed to remove all incoming HCHO. We show that a modified precision estimate accounting for regular instrument zeroing results in values of 0.09, 0.20, and 0.22 ppb at a 20 min integration time for the G2307, Ultra, and Pico, respectively. After applying standard addition and dynamic dilution calibrations, all instruments agreed within 13 % and were well correlated with each other (all r ≥ 0.90). TO-11A HCHO observations resulted in a normalized mean bias of −58 % compared to co-located Picarro G2307 measurements (r=0.62, slope = 0.38, int = 0.07 ppb HCHO). Using a 6-month deployment period in the Atlanta metropolitan area, we determined that the Picarro G2307 and Aeris units have sufficient accuracy and precision to capture the Atlanta spatial HCHO gradient. We find that midday HCHO concentrations have decreased by 22.3 % since 1999 in the city's urban core, and DNPH measurements at a nearby Photochemical Assessment Monitoring Station (PAMS) site show a greater decrease of 53 %.

Ambient volatile organic compounds in the Seoul metropolitan area of South Korea: Chemical reactivity, risks and source apportionment

The chemical reactivity, contribution of emission sources, and risk assessment of volatile organic compounds (VOCs) in the atmosphere of the Seoul metropolitan area (SMA) were analyzed. Datasets collected from 6 photochemical assessment monitoring stations (PAMS) of SMA from 2018 to 2021 were used. Alkenes and aromatics contributed significantly to ozone formation relative to the emission concentrations, and aromatics accounted for most of the secondary organic aerosols (SOA) formation in the SMA. The contributions of ozone and SOA formation were found to be notably higher at measurement stations in residential areas such as Guwol (GW) and Sosabon (SS) compared to other measurement stations. From the results of an emission source analysis, it was confirmed that anthropogenic sources such as combustion sources, vehicle exhaust, fuel evaporation, and solvent use had a significant effect at all measurement stations. Assessing the health risk, non-carcinogenic compounds were at acceptable level at all measurement stations. On the other hand, carcinogenic compounds were approaching risk level (10−4), thereby demanding immediate attention. The level of exposure to carcinogenic compounds increased by age group, and male was more vulnerable than female. It was found that SS had the highest level of exposure to carcinogens in the atmosphere of the population ages 60 or older. The health threat of the SMA population is expected due to direct exposure from inhalation of ambient toxic compounds and indirect exposure from ozone and PM2.5 formations through oxidation of VOCs. This study emphasizes the importance of addressing specific emission sources within the metropolitan area and developing comprehensive regional strategies to mitigate VOCs.

SR-Unet: A Super-Resolution Algorithm for Ion Trap Mass Spectrometers Based on the Deep Neural Network.

The mass spectrometer is an important tool for modern chemical analysis and detection. Especially, the emergence of miniature mass spectrometers has provided new tools for field analysis and detection. The resolution of a mass spectrometer reflects the ability of the instrument to discriminate between adjacent mass-to-charge ratio ions, and the higher the resolution, the better the discrimination of complex mixtures. Quadrupole ion traps are generally considered as a low-resolution mass spectrometry method, but they have gained wide attention and development in recent years because of their suitability for miniaturization and high qualitative capability. For an ion trap mass spectrometer, the mass sensitivity and resolution can be mutually constrained and need to be balanced by setting an appropriate scanning speed. In this study, a super-resolution U-net algorithm (SR-Unet) is proposed for ion trap mass spectrometry, which can estimate the possible ions from the overlapping ion peaks of low-resolution spectra and improve the equivalent resolution while ensuring sufficient sensitivity and analysis speed of the instrument. By determining the mass spectra of a linear ion trap mass spectrometer (LTQ XL) in Turbo and Normal scan modes, the same unit mass resolution as that at a scan speed of 16,667 Da/s was successfully obtained at 125,000 Da/s. Also, the experiments demonstrated that the algorithm is capable of the mass-to-charge ratio and instrument migration. SR-Unet can be migrated and applied to a miniature mass spectrometer for cruise detection of volatile organic compounds (VOCs), and the identification of VOC species in Photochemical Assessment Monitoring Stations (PAMS) was improved from 31 to 50 species with the same monitoring and analysis speed requirement. Further, super-unit mass resolution peptide detection was achieved on a miniature mass spectrometer with the help of the SR-Unet algorithm, which reduced the full width at half-maxima (FWHM) of bradykinin divalent ions (m/z 531) from 0.35 to 0.15 Da at a scan speed of 375 Da/s and improved the equivalent resolution to 3540. The proposed method provides a new idea to enhance the field mixture detection capability of miniature ion trap mass spectrometers.

Association between ambient BTEX mixture and neurological hospitalizations: A multicity time-series study in Taiwan

BackgroundBenzene, toluene, ethylbenzene, and xylenes, collectively known as BTEX, are hazardous chemical mixtures, and their neurological health effects have not been thoroughly evaluated. We examined the association between BTEX exposure and neurological hospital admissions. MethodsThis was a multicity time-series study conducted in five major Taiwanese cities. Daily hospital admission records for diseases of the nervous system from January 1, 2016, to December 31, 2017, were collected from the National Health Insurance Research Database. Ambient BTEX and criteria pollutant concentrations and weather factors were collected from Photochemical Assessment Monitoring Stations. We applied a Poisson generalized additive model (GAM) and weighted quantile sum regression to calculate city-specific effect estimates for BTEX and conducted a random-effects meta-analysis to pool estimates. ResultsWe recorded 68 neurological hospitalizations per day during the study period. The daily mean BTEX mixture concentrations were 22.5 µg/m3, ranging from 18.3 µg/m3 in Kaohsiung to 27.0 µg/m3 in Taichung, and toluene (13.6 µg/m3) and xylene (5.8 µg/m3) were the dominant chemicals. Neurological hospitalizations increased by an average of 1.6 % (95 % CI: 0.6–2.6 %) for every interquartile range (15.8 µg/m3) increase in BTEX at lag 0 estimated using a GAM model. A quartile increase in the weighted sum of BTEX exposure was associated with a 1.7 % (95 % CI: 0.6–2.8 %) increase in daily neurological hospitalizations. ConclusionWe found consistent acute adverse effects of BTEX on neurological hospitalizations in Taiwan, with toluene and xylene as the dominant chemicals. These findings aid the development of more targeted public health interventions.

Source-apportionment and spatial distribution analysis of VOCs and their role in ozone formation using machine learning in central-west Taiwan

This study assessed the machine learning based sensitivity analysis coupled with source-apportionment of volatile organic carbons (VOCs) to look into new insights of O3 pollution in Yunlin County located in central-west region of Taiwan. One-year (Jan 1 to Dec 31, 2021) hourly mass concentrations data of 54 VOCs, NOX, and O3 from 10 photochemical assessment monitoring stations (PAMs) in and around the Yunlin County were analyzed. The novelty of the study lies in the utilization of artificial neural network (ANN) to evaluate the contribution of VOCs sources in O3 pollution in the region. Firstly, the station specific source-apportionment of VOCs were carried out using positive matrix factorization (PMF)—resolving six sources viz. AAM: aged air mass, CM: chemical manufacturing, IC: Industrial combustion, PP: petrochemical plants, SU: solvent use and VE: vehicular emissions. AAM, SU, and VE constituted cumulatively more than 65% of the total emission of VOCs across all 10 PAMs. Diurnal and spatial variability of source-segregated VOCs showed large variations across 10 PAMs, suggesting for distinctly different impact of contributing sources, photo-chemical reactivity, and/or dispersion due to land-sea breezes at the monitoring stations. Secondly, to understand the contribution of controllable factors governing the O3 pollution, the output of VOCs source-contributions from PMF model along with mass concentrations of NOX were standardized and first time used as input variables to ANN, a supervised machine learning algorithm. ANN analysis revealed following order of sensitivity in factors governing the O3 pollution: VOCs from IC > AAM > VE ≈ CM ≈ SU > PP ≈ NOX. The results indicated that VOCs associated with IC (VOCs-IC) being the most sensitive factor which need to be regulated more efficiently to quickly mitigate the O3 pollution across the Yunlin County.

Sources-oriented contributions to ozone and secondary organic aerosol formation potential based on initial VOCs in an urban area of Eastern Asia

Over the past decades, the pollution of ozone (O3) and secondary organic aerosols (SOA) in the atmosphere has become a major concern worldwide due to their adverse effects on human health, air quality and climate. Volatile organic compounds (VOCs) are crucial precursors of O3 and SOA, but identifying the primary sources of VOCs that contribute to the formation of O3 and SOA has been challenging due to the rapid consumption of VOCs by oxidants in the air. To address this issue, a study was conducted in a Taipei urban area in Taiwan, where the hourly data of 54 VOC species were collected from March 2020 to February 2021 detected by Photochemical Assessment Monitoring Stations (PAMS). The initial mixing ratios of VOCs (VOCsini) were determined by combining the observed VOCs (VOCsobs) and the consumed VOCs resulting from photochemical reactions. Additionally, the ozone formation potential (OFP) and secondary organic aerosol formation potential (SOAFP) were estimated based on VOCsini. The OFP derived from VOCsini (OFPini) was found to exhibit a strong correlation with O3 mixing ratios (R2 = 0.82), whereas the OFP obtained from VOCsobs did not show such a correlation. Isoprene, toluene and m,p-xylene were the top three species contributing to OFPini, while toluene and m,p-xylene were the top two contributors to SOAFPini. Positive matrix factorization analysis revealed that biogenic, consumer/household products, and industrial solvents were the major contributors to OFPini in four seasons, and SOAFPini mostly came from consumer/household products and industrial solvents. This study highlights the importance of considering photochemical loss caused by different VOCs reactivity in the atmosphere when evaluating OFP and SOAFP. Moreover, it emphasizes the need to prioritize controlling the sources emitting the dominant VOC precursors of O3 and SOA to effectively alleviate the scenarios of elevated O3 and particulate matter.

Developing the Maximum Incremental Reactivity for Volatile Organic Compounds in Major Cities of Central‐Eastern China

AbstractThe Chinese government has identified volatile organic compounds (VOCs) management as a key priority in the fourteenth Five‐Year Plan (2021–2025) to alleviate ground‐level ozone (O3) air pollution. To provide scientific support for VOCs management, we developed the localized maximum incremental reactivity (MIR) for 57 VOCs species (prescribed by the Photochemical Assessment Monitoring Stations (PAMS)) in eight representative cities and averaged urban conditions over Central‐Eastern China, with application of the Master Chemical Mechanism box model coupled with solid observational constraints. Though the exact environmental conditions differ among cities, all of them are in VOCs‐limited O3 formation regime, underlining the importance of VOCs to O3 formation. The MIRs constructed based on regional average scenarios are well representative of those constructed based on individual cities, with Guangzhou as an exception due to its vast variance in chemical environments. The localized MIRs displayed the same overall pattern as the U.S. MIRs, but differed largely with respect to a few species (especially alkenes), owing to a combined influence of many factors. We applied the localized MIRs to quantify the concentration‐weighted ozone formation potential (OFP), which elucidate the importance of aromatics to O3 formation in the Chinese metropolitan areas. The top 10 key VOC species together with their explicitly tracked emission sources were determined, which could offer references for the formulation of effective control policies. The localized MIRs developed in this study can be applied to quantify OFPs for VOCs in Chinese cities, which has a great significance to VOCs management and O3 pollution control.

Characteristics of Photochemical Reactions with VOCs Using Multivariate Statistical Techniques on Data from Photochemical Assessment Monitoring Stations

This study assesses the concentrations of the 54 ozone precursors (all being volatile organic compounds (VOCs)) detected at the four photochemical assessment monitoring stations that are part of the air quality monitoring network in the Kaohsiung-Pingtung area in Taiwan. Factor and cluster analyses of the multivariate statistical analysis are performed to explore the interrelationship among the 10 VOCs of relatively higher concentrations selected from the 54 ozone precursors to identify significant factors affecting ozone pollution levels in the study area. Moreover, the multivariate statistical analysis can faithfully reflect why the study area has been affected by photochemical pollution. First, results of the factor analysis suggest that the factors affecting how photochemical reactions occur in the study area can be divided into the following: “pollution from mobile sources”, “pollution from stationary sources”, and “pollution from energy sources”. Among them, mobile sources have the greatest impact on photochemical pollution levels. Second, the impacts of photochemical pollution on air quality in the study area can be classified into four clusters via cluster analysis. Each cluster represents how the 10 VOCs affect air quality, with different characteristics, and how they contribute to photochemical pollution in the study area. If there are more types and samples of photochemical pollutants when performing a multivariate statistical analysis, the analysis results will be more stable. This study adopts data on VOC monitoring over a period of nearly two years, which can effectively improve the validity and reliability of the factor analysis results, while helping environmental agencies review the effectiveness of air quality management in the future and serving as reference for the effectiveness of reducing photochemical pollution in the atmosphere.

Inter-comparisons of VOC oxidation mechanisms based on box model: A focus on OH reactivity

Volatile organic compounds (VOCs) oxidation processes play a very important role in atmospheric chemistry, and the chemical reactions are expressed in various manners in chemical mechanisms. To gain an improved understanding of VOCs evolution during oxidation processes and evaluate the discrepancies of VOCs oxidation schemes among different mechanisms, we used the total VOC reactivity as a diagnostic and evaluated tool to explore the differences for six widely used chemical mechanisms. We compared the total VOC reactivity evolution under high-NOx conditions for several sets of precursors, including n-pentane, toluene, ethene, isoprene and a mixture of 57 Photochemical Assessment Monitoring Stations (PAMS) species in a 0-D photochemical box model. Inter-comparison of total VOC reactivity of individual precursor simulations showed discrepancies to different extent of the oxidation schemes among the studied mechanisms, which are mainly attributed to the different lumping approaches for organic species. The PAMS simulation showed smaller discrepancy than individual precursor cases in terms of total VOC reactivity. SAPRC07 and RACM2 performances are found to better match the MCM for simulation of total VOC reactivity. Evidences suggest that the performance in simulating secondary organic products, OH concentrations and NOx concentrations are related to the OH reactivity discrepancies among various chemical mechanisms. Information in this study can be used in selection of chemical mechanisms to better model OH reactivity in different environments. The results in this study also provide directions to further improve the ability in modelling total VOC reactivity with the chemical mechanisms.

A method for identifying critical time windows of maternal air pollution exposures associated with low birth weight in offspring using massive geographic data.

Associations between maternal exposures to air pollutants and low birth weight (LBW) in offspring varied when different exposure windows were considered. Methods used in previous studies lacked flexibility in delineating exposure windows and did not consider time periods before conception, which may restrict the discoveries of critical exposure windows. This study introduces a novel method to identify critical windows of maternal air pollution exposures associated with LBW in offspring using massive georeferenced data. Through a case-control study based on birth data (94,106 LBW cases and 376,424 controls) and air quality monitoring data (367 chemicals) in Texas during 1996-2008, this study used the average ambient concentration measured by the monitoring site closest to the residence location of a mother during a time window as the maternal exposure to a specific chemical during that exposure window. Binary logistic regression was utilized to estimate air pollutant-LBW associations in different exposure windows. The odds ratios (ORs) were adjusted for child's sex, gestational weeks, maternal age, race/ethnicity, and education. The adjusted ORs were plotted against the exposure window series of different sizes for each chemical, aiming at interactively visualizing and exploring the critical exposure windows across multiple temporal scales. This study identifies ten chemicals and seventeen corresponding critical exposure windows where strong air pollutant-LBW associations are detected. The ten identified chemicals are benzaldehyde, sum of Photochemical Assessment Monitoring Stations (PAMS) target compounds, n-undecane, m-tolualdehyde, organic carbon fraction 2 (OC2), ethylene dibromide, valeraldehyde, propionaldehyde, 4-methyl-1-pentene, and zirconium. Nine critical exposure windows involving six chemicals start more than fivemonths prior to conception, seven windows involving five chemicals commence in the second and/or third trimester of pregnancy, and the remaining one window is located in other time periods. The novel method reveals a number of critical time windows of maternal exposure to ten chemicals that are positively associated with LBW in offspring. These ten chemicals were identified as LBW risk factors for the first time. Additional studies with more data are needed to validate the results in the future.

Update on volatile organic compound (VOC) source profiles and ozone formation potential in synthetic resins industry in China

The synthetic resin industry plays an important role in Volatile organic compounds (VOCs) emissions from industrial sources. However, owing to various products and their different emission characteristics, it is extremely difficult to study the source profiles of synthetic resins. In this study, the product-based pollution characteristics of VOCs from eight synthetic resin enterprises were investigated in Shanghai, China. Up to 133 VOCs were identified, including 106 based on the Photochemical Assessment Monitoring Stations (PAMS) and the Toxic Organics (TO-15) methods, and the remaining 27 were identified based on the new mass spectrometry analysis method. Aromatics (39.7%) and oxygenated VOCs (29.9%) accounted for a relatively high proportion in the synthetic resin industry. The product-based source profiles of each process unit are compiled. Generally, 1,4-dioxane, methyl isobutyl ketone, toluene, benzene, styrene, propane, and dichloromethane are the most abundant species in synthetic resin. Furthermore, the product-based ozone formation potentials (OFPs) and sources reactivity (SR) were calculated, the synthetic resin industry SR range from 0.3 g g−1 to 4.6 g g−1. Results suggest that toluene, benzene, styrene, propylene, ethylene, and oxygenated VOCs (including 1,4-dioxane, methyl isobutyl ketone, and aldehyde) should be preferentially controlled to reduce the OFPs. A three-level classification was established to evaluate the degree of photochemical pollution in different industries. Emission factors were calculated and ranked for eight synthetic resins. A VOC emission inventory of Chinese synthetic resin from 2005 to 2018 was compiled. It is estimated that the Chinese synthetic resin emitted 23.96 Gg of VOCs in 2018. In this study, a product-based VOC source profile and emission inventory of the synthetic resin industry were established for the first time. Finally, combined with product types, processes, and processing equipment, feasible recommendations for reducing VOC emissions in the synthetic resin industry are proposed.

Study on Air Pollution Behavior of VOCs with Photochemical Monitoring Stations Using EGARCH Model in Southern Taiwan

This study adopted the exponential generalized autoregressive conditional heteroscedasticity (EGARCH) model to examine the 10 ozone precursors of the highest concentrations among the 54 that were assessed over a number of years at the four photochemical assessment monitoring stations (PAMSs) in the Kaohsiung–Pingtung Area in Taiwan. First, the 10 ozone precursors, which were all volatile organic compounds (VOCs), were analyzed using the factor analyses in multiple statistical analyses that had the most significant impact on the area’s ozone formation: mobile pollution factor, which included 1,2,4-Trimethylbenzene (C9H12), toluene (C7H8), and Isopropyl benzene (C9H12). Then, taking into consideration that the number sequences might be affected by standardized residuals, this study applied the vector autoregressive moving average-EGARCH (VARMA-EGARCH) model to analyze the correlation between the three VOCs under different polluting activities. The VARMA-EGARCH model in this research included dummy variables representing changing points of variance structures in the variance formula to predict the conditional variance. This process proved able to effectively estimate the relevant coefficients of the three VOCs’ dynamic conditions that changed with time. The model also helped to prevent errors from occurring when estimating the conditional variance. Based on the testing results, this study determined the VARMA(2,1)-EGARCH(1,0) as the most suitable model for exploring the correlation between the three VOCs and meteorological phenomena, as well as the interplay between them in regard to interaction and formation. With the most representative of the three, toluene (TU), as the dependent variable and 1,2,4-Trimethylbenzene (TB) and Isopropyl benzene (IB) as the independent variables, this study found it impossible to calculate the TU concentration with TB and IB concentrations in the same period; estimations of TB and IB concentrations with a period of lag time were required because TU was mainly contributed by automobiles and motorcycles in Kaohsiung. TB and IB resulted from other stationary pollution sources in the region besides cars and motorbikes. When TU was evenly distributed and stayed longer in the atmosphere, the TB and IB concentrations were lower, so distribution conditions and concentrations could not be used to effectively estimate the concentration of toluene. This study had to wait until the next period, or when stationary pollution sources started producing TB and IB of higher concentrations during the daytime, in order to estimate the TU concentrations in a better photochemical situation.

Volatile Organic Compounds Monitored Online at Three Photochemical Assessment Monitoring Stations in the Pearl River Delta (PRD) Region during Summer 2016: Sources and Emission Areas

Volatile organic compounds (VOCs) were monitored online at three photochemical assessment monitoring stations (MDS, WQS and HGS) in the Pearl River Delta region during the summer of 2016. Measured levels of VOCs at the MDS, WQS and HGS sites were 34.78, 8.54 and 8.47 ppbv, respectively, with aromatics and alkenes as major ozone precursors and aromatics as major precursors to secondary organic aerosol (SOA). The positive matrix factorization (PMF) model revealed that VOCs at the sites mainly came from vehicle exhaust, petrochemical industry, and solvent use. Vehicle exhaust and industrial processes losses contributed most to ozone formation potentials (OFP) of VOCs, while industrial processes losses contributed most to SOA formation potentials of VOCs. Potential source contribution function (PSCF) analysis revealed a north-south distribution for source regions of aromatics occurring at MDS with emission sources in Guangzhou mainly centered in the Guangzhou central districts, and source regions of aromatics at WQS showed an east-west distribution across Huizhou, Dongguan and east of Guangzhou, while that at HGS showed a south-north distribution across Guangzhou, Foshan, Zhaoqing and Yangjiang. This study demonstrates that multi-point high time resolution data can help resolve emission sources and locate emission areas of important ozone and SOA precursors.

Association of cardiorespiratory hospital admissions with ambient volatile organic compounds: Evidence from a time-series study in Taipei, Taiwan

As important precursors of ozone and secondary organic aerosols, the harmful impact of exposure to ambient volatile organic compounds (VOCs) is of public health interest. However, few studies have investigated the health risks of numerous individual VOC species. This study linked the daily concentrations of 54 C2–C11 VOC species monitored from the Wanhua Photochemical Assessment Monitoring Station and hospital admissions for cardiorespiratory diseases in Taipei, Taiwan, from the National Health Insurance Research Database. A standard time-series approach entailing a series of sensitivity analyses was applied to investigate the short-term health risks of exposure to VOC subgroups and species. Consistent associations of all VOC subgroups and main species with chronic obstructive pulmonary disease (COPD) hospitalizations were demonstrated. In addition, associations of the C5–C6 alkanes, C2–C3 alkenes, toluene, and xylene with asthma hospitalizations were found, as were associations of aromatic hydrocarbons with hospitalizations for heart failure. An interquartile range increase in total VOC exposure at lag0 day (102.6 parts per billion carbon) was associated with increments of 1.84% (95% confidence interval: 0.54%–3.15%), 1.65% (0.71%–2.60%), and 1.21% (0.36%–2.07%) in hospitalizations for asthma, COPD, and heart failure, respectively. The effect estimates were robust with data excluding extreme values, the second pollutant adjustment for PM2.5 and O3, and the Bonferroni correction. The associations of ambient VOC exposure with cardiorespiratory hospitalizations in Taipei serve as a reference for VOC regulations and ozone control strategies.

Profiles and Source Apportionment of Nonmethane Volatile Organic Compounds in Winter and Summer in Xi’an, China, based on the Hybrid Environmental Receptor Model

Summer and winter campaigns for the chemical compositions and sources of nonmethane hydrocarbons (NMHCs) and oxygenated volatile organic compounds (OVOCs) were conducted in Xi’an. Data from 57 photochemical assessment monitoring stations for NMHCs and 20 OVOC species were analyzed. Significant seasonal differences were noted for total VOC (TVOC, NMHCs and OVOCs) concentrations and compositions. The campaign-average TVOC concentrations in winter (85.3 ± 60.6 ppbv) were almost twice those in summer (47.2 ± 31.6 ppbv). Alkanes and OVOCs were the most abundant category in winter and summer, respectively. NMHCs, but not OVOCs, had significantly higher levels on weekends than on weekdays. Total ozone formation potential was higher in summer than in winter (by 50%) because of the high concentrations of alkenes (particularly isoprene), high temperature, and high solar radiation levels in summer. The Hybrid Environmental Receptor Model (HERM) was used to conduct source apportionment for atmospheric TVOCs in winter and summer, with excellent accuracy. HERM demonstrated its suitability in a situation where only partial source profile data were available. The HERM results indicated significantly different seasonal source contributions to TVOCs in Xi’an. In particular, coal and biomass burning had contributions greater than half in winter (53.4%), whereas traffic sources were prevalent in summer (53.1%). This study’s results highlight the need for targeted and adjustable VOC control measures that account for seasonal differences in Xi’an; such measures should target not only the severe problem with VOC pollution but also the problem of consequent secondary pollution (e.g., from ozone and secondary organic aerosols).

Spatial Distribution, Source Apportionment, Ozone Formation Potential, and Health Risks of Volatile Organic Compounds over a Typical Central Plain City in China

The profiles, contributions to ozone formation, and associated health risks of 56 volatile organic compounds (VOCs) species were investigated using high time resolution observations from photochemical assessment monitoring stations (PAMs) in Luoyang, China. The daily averaged concentration of total VOCs (TVOCs) was 21.66 ± 10.34 ppbv in urban areas, 14.45 ± 7.40 ppbv in suburbs, and 37.58 ± 13.99 ppbv in an industrial zone. Overall, the VOCs levels in these nine sites followed a decreasing sequence of alkanes > aromatics > alkenes > alkyne. Diurnal variations in VOCs exhibited two peaks at 8:00–9:00 and 19:00–20:00, with one valley at 23:00–24:00. Source apportionment indicated that vehicle and industrial emissions were the dominant sources of VOCs in urban and suburban sites. The industrial site displayed extreme levels, with contributions from petrochemical-related sources of up to 38.3%. Alkenes and aromatics displayed the highest ozone formation potentials because of their high photochemical reactivity. Cancer and noncancer risks in the industrial site were higher than those in the urban and suburban areas, and USEPA possible risk thresholds were reached in the industrial site, indicating PAMs VOC–related health problems cannot be ignored. Therefore, vehicle and industrial emissions should be prioritized when considering VOCs and O3 control strategies in Luoyang.

A comprehensive study on ozone pollution in a megacity in North China Plain during summertime: Observations, source attributions and ozone sensitivity

Tropospheric ozone (O3) pollution has been becoming prominent in North China Plain (NCP) in China since last decade. In order to clarify the source contribution and formation mechanism of O3, the critical precursors of volatile organic compounds (VOCs) were measured with both on-line and off-line methods in Luoyang City in summer of 2019. The concentrations of nitrogen oxides (NOx, sum of NO and NO2) and O3 were simultaneously monitored. Fifty-seven VOCs measured in U.S. Photochemical Assessment Monitoring Station (PAMS) showed daily concentrations in a range of 14.5 ± 5.33 to 29.2 ± 11.2 ppbv in Luoyang, which were comparable with those in other Chinese megacities. The mass compositions of VOCs were determined, with comparatively low proportions of alkanes (<50%) but high fractions of photoreactive alkenes and alkyne. Source apportionment of VOCs was conducted by Hybrid Environmental Receptor Model (HERM). The results indicated that industrial (38.5%) and traffic (32.0%) were the two dominated pollution sources of VOCs in the urban, while the biogenic and residential sources had contributions of 15.8% and 13.8%, respectively. To further measure the O3 formation sensitivity and its source attribution, the WRF-CHEM model was adopted in this study. The variation of O3 between the observation and the stimulation using the local emission inventory showed an index of agreement (IOA) of 0.85. The simulation conducted by WRF-CHEM indicated an average of 43.5% of the O3 was associated with the regional transportation, revealing the importance of inter-regional prevention and control policy. Traffic and biogenic emissions were the two major pollution sources to an O3 episode occurred from July 21 to July 27, 2019 (when O3 concentration over 150 μg m−3) in Luoyang, with average contributions of 22.9% and 18.3%, respectively. The O3 isopleths proved that its formation in the atmosphere of Luoyang was in transitional regime and collectively controlled by both VOCs and NOx. This was different from the observations in main cities of NCP before implantations of strict emission controls. The isopleths additionally designated that the O3 formation regime would move forward or shift to NOx regime after a reduction of over 45% during the episode. Similar patterns were also reported in other Chinese megacities such as Beijing and Shanghai, due to the tightening of the NOx control policies. Our results do support that the simultaneous controls of NOx and VOCs were effective in reductions of tropospheric O3 in Luoyang. Meanwhile, joint regional control policies on the emissions of NOx and VOCs can potentially overwhelm the current O3 pollutions in China.

An automated common algorithm for planetary boundary layer retrievals using aerosol lidars in support of the U.S. EPA Photochemical Assessment Monitoring Stations Program.

A unique automated planetary boundary layer (PBL) retrieval algorithm is proposed as a common cross-platform method for use with commercially available ceilometers for implementation under the redesigned U.S. Environmental Protection Agency Photochemical Assessment Monitoring Stations program. This algorithm addresses instrument signal quality and screens for precipitation and cloud layers before the implementation of the retrieval methodology using the Haar wavelet covariance transform method. Layer attribution for the PBL height is supported with the use of continuation and time-tracking parameters, and uncertainties are calculated for individual PBL height retrievals. Commercial ceilometer retrievals are tested against radiosonde PBL height and cloud-base height during morning and late afternoon transition times, critical to air quality model prediction and when retrieval algorithms struggle to identify PBL heights. A total of 58 radiosonde profiles were used and retrievals for nocturnal stable layers, residual layers and mixing layers were assessed. Overall good agreement was found for all comparisons with one system showing limitations for the cases of nighttime surface stable layers and daytime mixing layer. It is recommended that nighttime shallow stable layer retrievals be performed with a recommended minimum height or with additional verification. Retrievals of residual layer heights and mixing layer comparisons revealed overall good correlations to radiosonde heights (correlation coefficients, r2, ranging from 0.89 - 0.96 and bias ranging from ~ -131 to +63 m, and r2 from 0.88 - 0.97 and bias from -119 to +101 m, respectively).

Decadal Trends of Speciated Non‐methane Hydrocarbons in Taipei

AbstractSelected non‐methane hydrocarbons (NMHCs) obtained from long‐term operation of the Photochemical Assessment Monitoring Stations (PAMS) in Taipei allowed for the assessment of the effectiveness of emission control measures on ozone precursors from 2007 to 2016. Despite the very pronounced diurnal and seasonal cycles of all the 51 target compounds, almost all species showed various degrees of declining trends over the decade. When dividing the 51 compounds into five groups of alkanes, alkenes, ethyne, aromatics, and isoprene, the decadal trends are assessed as −0.7 ± 0.8, −0.3 ± 0.1, −0.02 ± 0.14, −1.9 ± 1.2, and − 0.09 ± 0.02 ppbC year−1, respectively. Meanwhile, as evidenced by multiple NMHC ratios as effective indicators of atmospheric photochemical conditions, a trend of gradual lessening in the degree of photochemistry over time was noticed. Air masses in Taipei are suggested to be increasingly more contributed by local emissions and less affected by mixing with transboundary or long‐range transported influences.