Temporal evolution of speciated volatile organic compound (VOC) emissions from solvent use sources in the Pearl River Delta Region, China (2006-2019).

Volatile organic compounds (VOCs) emitted from solvent use sources constitute an important part of ozone (O3) and secondary organic aerosols (SOA) in the Pearl River Delta (PRD) region, China. While stringent control measures targeting VOCs have been implemented in recent years, an assessment of historical trends is imperative to evaluate their effectiveness. In this study, trends of VOC emissions, compositions, and reactivity from solvent use sources in the PRD region from 2006 to 2019 were estimated using a developed methodology, which considered the improvement of manufacturing equipment and removal efficiency. Results showed that total VOC emissions from solvent use sources displayed an overall increase from 277 kt in 2006 to 400 kt in 2019 despites some fluctuations, with metal products contributing more than 20 % each year. Aromatics and oxygenated VOCs (OVOCs) accounted for over 70 % of total VOC emissions, increasing by 21 kt and 52 kt respectively. OFP and SOAFP increased by 40 % and 23 % respectively from 2006 to 2019. Specific aromatic species, including m/p-xylene, toluene, 1,2,3,5-tetramethylbenzene, o-xylene and ethylbenzene were identified as key species in both VOC emission amount and reactivity. This study aims to facilitate the understanding of VOC emission evolution from solvent use sources in the region and provide insights into the impact of enacted measures, aiding in the future development of more targeted and efficient strategies in the PRD region.

[Driving Forces and Mitigation Potential of CO2 Emissions for Ship Transportation in Guangdong Province, China].

Ships are important sources of carbon dioxide (CO2) emissions in Guangdong Province. The study of historical evolutions, drivers, and projected pathways of CO2 emissions can provide scientific support for the development of carbon peaking and carbon neutral strategies in Guangdong Province. The emission factor method, log-average index (LMDI) method, and scenario analysis method were adopted to estimate CO2 emissions, identify the drivers, and explore the mitigation potential from ships in Guangdong Province, separately. The results showed that:① CO2 emissions from ships in Guangdong Province increased from 3.319 4 million tons to 6.392 9 million tons from 2006 to 2020, with dry bulk carriers and container ships being the main ship types causing the increase in emissions. ② The positive drivers of CO2 emissions from ships in Guangdong Province from 2006 to 2020 were transport intensity (51%) and economic factors (49%), and the negative drivers were energy intensity (93%) and cargo class structure (7%). ③ Carbon peaking would not be reached by 2030 if Guangdong Province maintains the current policy (baseline scenario) for ship transportation. ④ Simultaneous optimization of the energy structure and promotion of the energy intensity (energy-efficient and low-carbon scenario) had a 56.51% potential to reduce CO2 emissions from ships compared to the baseline scenario. This can provide scientific support for Guangdong Province to develop a carbon peaking and carbon neutral control strategy for the shipping industry.

[Evolution Characteristics and Driving Forces of Carbon Dioxide Emissions and Sinks in the Pearl River Delta Region, China].

With the rapid economic and population growth, the Pearl River Delta(PRD) Region is one of the regions in China under the greatest pressure to be carbon neutral. This study analyzed the historical evolution characteristics of the carbon dioxide(CO2) emissions and sinks from 2006-2020 and identified the key drivers of the CO2 emissions and sinks based on the exponential decomposition method. The results showed that:① from 2006 to 2020, the total carbon emissions in the PRD Region increased from 218.22 million tons to 366.30 million tons, showing a fluctuating and rising evolution characteristic, with an overall increase of 67.86%. The carbon emission had not yet reached a peak. ② From 2006 to 2020, the total carbon sinks in the PRD Region decreased from 15.67 million tons to 15.53 million tons, showing a trend of fluctuation and decline, with an overall decrease of 0.94%. The carbon sinks were far lower than the carbon emissions, and there was still a large gap between carbon neutrality. ③ The main carbon emission sectors in the PRD Region were the energy sector(40.38%) and industrial sector(26.33%), and the carbon sinks mainly came from forestland(67.92%) and farmland(18.09%). ④ During the period from the "11th Five-Year Plan" to the "13th Five-Year Plan," the main positive driving factors for carbon emissions were economic growth and population size, whereas the main negative driving factor was energy intensity(energy use per unit GDP). However, since the "13th Five-Year Plan," the CO2 emission reduction potential released by reducing energy intensity has been weakening. In the future, the PRD Region needs to address the negative driving potential of the structural adjustment in energy, industry, transportation, and land use. ⑤ During the period from the "11th Five-Year Plan" to the "13th Five-Year Plan," the main positive driving factor for the carbon sink was the green scale, which was conducted by the increase in urban green space during the "11th Five-Year Plan." The main negative driving factor for the carbon sink was the carbon sink coefficient, which was caused by the natural disaster-induced yield reductions in crops with a high carbon sink coefficient, such as rice. Green space structure adjustment should be emphasized in the future. This study can provide scientific support for developing robust carbon-neutral policies in the PRD Region.

[Evolution Characteristics of Atmospheric Formaldehyde Emissions in Guangdong Province from 2006 to 2020].

Atmospheric formaldehyde, a key precursor for ozone (O3) and secondary PM2.5, is carcinogenic and plays an important role in atmospheric photochemistry and the formation of secondary pollution. However, the lack of understanding of the emission sources of atmospheric formaldehyde limits the study on the formation mechanism of secondary pollution and the formulation of pollution control strategies. This study used the emission factor and source profile methods to establish the emission inventories of formaldehyde in Guangdong Province from 2006 to 2020 and identified the main emission sources of formaldehyde and spatial and temporal evolution characteristics. The results showed that the formaldehyde emissions in Guangdong Province fluctuated in the range of 39000-56000 tons during 2006 to 2020, exhibiting a very weak downward trend. Biomass combustion is an important source of formaldehyde emission in Guangdong Province, of which the contribution decreased from 58% in 2006 to 27% in 2020 owing to effective control measures implemented in Guangdong Province. The solvent use source became the predominant emission source of formaldehyde in 2020 by contributing up to 28%, primarily through plastic products and asphalt paving sources. The construction machinery and trucks fueled by diesel were important contributors of formaldehyde emissions from mobile sources. Although the formaldehyde emissions in the Pearl River Delta and the non-Pearl River Delta were equivalent, the spatial distributions showed that formaldehyde emission hotspots were concentrated in the center of the Pearl River Delta and the eastern and western areas of the non-Pearl River Delta. This was primarily because the solvent use and mobile sources were the main sources of formaldehyde emissions in the Pearl River Delta, whereas the biomass combustion source was the dominant source in the non-Pearl River Delta. Therefore, the formaldehyde emission mitigations of the industrial and mobile sources in the central region of the Pearl River Delta and the biomass combustion source in the western area of Guangdong should be further strengthened in the future.

Direct identification of total and missing OH reactivities from light-duty gasoline vehicle exhaust in China based on LP-LIF measurement.

Considerable efforts have been devoted to characterising the chemical components of vehicle exhaust. However, these components may not accurately reflect the contribution of vehicle exhaust to atmospheric reactivity because of the presence of species not accounted for ("missing species") given the limitations of analytical instruments. In this study, we improved the laser photolysis-laser-induced fluorescence (LP-LIF) technique and applied it to directly measure the total OH reactivity (TOR) in exhaust gas from light-duty gasoline vehicles in China. The TOR for China I to VI-a vehicles was 15.6, 16.3, 8.4, 2.6, 1.5, and 1.6 × 104 sec-1, respectively, reflecting a notable drop as emission standards were upgraded. The TOR was comparable between cold and warm starts. The missing OH reactivity (MOR) values for China I to IV vehicles were close to zero with a cold start but were much higher with a warm start. The variations in oxygenated volatile organic compounds (OVOCs) under different emission standards and for the two start conditions were similar to those of the MOR, indicating that OVOCs and the missing species may have similar production processes. Online measurement revealed that the duration of the stable driving stage was the primary factor leading to the production of OVOCs and missing species. Our findings underscore the importance of direct measurement of TOR from vehicle exhaust and highlight the necessity of adding OVOCs and other organic reactive gases in future upgrades of emission standards, such that the vehicular contribution to atmospheric reactivity can be more effectively controlled.

Developing a model-ready highly resolved HONO emission inventory in Guangdong using domestic measured emission factors.

Nitrous acid (HONO) plays an important role in the budget of hydroxyl radical (OH) in the atmosphere. However, current chemical transport models (CTMs) typically underestimate ambient concentrations of HONO due to a dearth of high resolution primary HONO emission inventories. To address this issue, we have established a highly resolved bottom-up HONO emission inventory for CTMs in Guangdong province, utilizing the best available domestic measured emission factors and newly obtained activity data. Our results indicate that emissions from various sources in 2020, including soil, on-road traffic, non-road traffic, biomass burning, and stationary combustion, were estimated at 21.5, 10.0, 8.2, 2.5, and 0.7 kt, respectively. Notably, the HONO emissions structure differed between the Pearl River Delta (PRD) and the non-PRD regions. Specifically, traffic sources were the dominant contributors (62 %) to HONO emissions in the PRD, whereas soil sources accounted for the majority (65 %) of those in the non-PRD. Among on-road traffic sources, diesel vehicles played a significant role, contributing 99.7 %. Comparisons with previous methods suggest that HONO emissions from diesel vehicles are underestimated by approximately 2.5 times. Higher HONO emissions, dominated by soil emissions, were observed in summer months, particularly in August. Furthermore, diesel vehicle emissions were pronounced at night, likely contributing to the nighttime accumulation of HONO and the morning peak of OH. The emission inventories developed in this study can be directly applied to widely used CTMs, such as CMAQ, CAMx, WRF-Chem, and NAQPMS, to support the simulation of OH formation and secondary air pollution.

Characterizing Operating Condition-Based Formaldehyde Emissions of Light-Duty Diesel Trucks in China Using a PEMS-HCHO System.

Formaldehyde (HCHO) plays a critical role in atmospheric photochemistry and public health. While existing studies have suggested that vehicular exhaust is an important source of HCHO, the operating condition-based diesel truck HCHO emission measurements remain severely limited due to the limited temporal resolution and accuracy of measurement techniques. In this study, we characterized the second-by-second HCHO emissions from 29 light-duty diesel trucks (LDDTs) in China over dynamometer and real-world driving tests using a portable online HCHO emission measurement system (PEMS-HCHO), considering various operating conditions. Our results suggested that the HCHO emissions from LDDTs might be underestimated by the widely used offline DNPH-HPLC method. The HCHO emissions at a 200 s cold start from China V LDDT can be up to 50 mg/start. Different driving conditions over dynamometer and real-world driving tests led to a 2-4 times difference in the HCHO emission factors (EFs). Under real-world hot-running conditions, the HCHO EFs of China III, IV, V, and VI LDDTs were 43.5 ± 35.7, 10.6 ± 14.2, 8.8 ± 5.1, and 3.2 ± 1.2 mg/km, respectively, which significantly exceeded the latest California low emission vehicle III HCHO emission standard (2.5 mg/km). These findings highlighted the significant impact of vehicle operating conditions on HCHO emissions and the urgency of regulating HCHO emissions from LDDTs in China.

VOC emission caps constrained by air quality targets based on response surface model: A case study in the Pearl River Delta Region, China.

Because of the recent growth in ground-level ozone and increased emission of volatile organic compounds (VOCs), VOC emission control has become a major concern in China. In response, emission caps to control VOC have been stipulated in recent policies, but few of them were constrained by the co-control target of PM2.5 and ozone, and discussed the factor that influence the emission cap formulation. Herein, we proposed a framework for quantification of VOC emission caps constrained by targets for PM2.5 and ozone via a new response surface modeling (RSM) technique, achieving 50% computational cost savings of the quantification. In the Pearl River Delta (PRD) region, the VOC emission caps constrained by air quality targets varied greatly with the NOx emission reduction level. If control measures in the surrounding areas of the PRD region were not considered, there could be two feasible strategies for VOC emission caps to meet air quality targets (160 µg/m3 for the maximum 8-hr-average 90th-percentile (MDA8-90%) ozone and 25 µg/m3 for the annual average of PM2.5): a moderate VOC emission cap with <20% NOx emission reductions or a notable VOC emission cap with >60% NOx emission reductions. If the ozone concentration target were reduced to 155 µg/m3, deep NOx emission reductions is the only feasible ozone control measure in PRD. Optimization of seasonal VOC emission caps based on the Monte Carlo simulation could allow us to gain higher ozone benefits or greater VOC emission reductions. If VOC emissions were further reduced in autumn, MDA8-90% ozone could be lowered by 0.3-1.5 µg/m3, equaling the ozone benefits of 10% VOC emission reduction measures. The method for VOC emission cap quantification and optimization proposed in this study could provide scientific guidance for coordinated control of regional PM2.5 and O3 pollution in China.

Fine particulate pollution driven by nitrate in the moisture urban atmospheric environment in the Pearl River Delta region of south China.

To identify potential sources of fine particles (PM2.5, with aerodynamic diameter (Da) ≤ 2.5 µm) in urban Dongguan of south China, a comprehensive campaign was carried out in the whole 2019. Hourly PM2.5 and its dominant chemical components including organic carbon (OC), elemental carbon (EC), water-soluble inorganic ions (WSIIs) and thirteen elements were measured using online instruments. Gaseous pollutants including NH3, HNO3, NO2, NO and O3 and meteorological parameters were also synchronously measured. PM2.5 was dominated by carbonaceous aerosols in summer and by WSIIs in the other seasons. PM2.5 and its dominant chemical components mostly peaked around noon (10:00-14:00 LST). Furthermore, high PM2.5 levels during the daytime were closely related with the increased NO3- levels. The high mass concentrations of NO3- in urban Dongguan during the daytime were likely related with regional transport of NO3- from suburban Dongguan, which was originated from the reaction between NO2 and O3 under the moisture condition during the nighttime. Seven major source factors for PM2.5 including secondary sulfate, ship emission, traffic emission, secondary nitrate, industrial processes, soil dust and coal combustion were identified by positive matrix factorization (PMF) analysis, which contributed 26 ± 14%, 16 ± 16%, 16 ± 10%, 14 ± 11%, 12 ± 11%, 8 ± 6% and 8 ± 6%, respectively, to annual PM2.5 mass concentration. Although secondary sulfate contributed much more than secondary nitrate to PM2.5 on annual basis, the latter exceeded the former source factor when daily PM2.5 mass concentration was higher than 60 µg m-3, indicating the critical role nitrate played in PM2.5 episode events.

Measurement-based intermediate volatility organic compound emission inventory from on-road vehicle exhaust in China.

Intermediate volatility organic compounds (IVOCs) have great potential to form secondary organic aerosols (SOA) in the atmosphere. Thus, a high-resolution IVOC emission inventory is essential for the accurate simulation of SOA formation. This study developed the first nationwide on-road vehicular IVOC emission inventory in China based on localized measurement of the IVOC emission factors and volatility distributions for various vehicle types. The total vehicular IVOC emissions in China in 2019 were estimated to be 241.2 Gg. Heavy-duty trucks, light-duty trucks, and light-duty passenger vehicles contributed the most, accounting for 47.6%, 24.6%, and 16.9% of total vehicular IVOC emissions, respectively. Although much higher in number, gasoline vehicles contributed 15.0%, which was far less than the contribution of diesel vehicles. The two peaks in volatility bins B12-B13 and B16-B17 accounted for 42.2% and 23.7% of the total IVOC emissions, respectively. By gridding the emission inventory into a relatively high resolution of 0.1° × 0.1°, high-emission areas and hotspots were clearly identified. In general, eastern China had substantially higher vehicular IVOC emissions than western China. High-emission areas with emission intensity >10 Mg·grid-1 covered most of the North China Plain, Yangtze River Delta, and Pearl River Delta. The emission intensity over the downtown areas of Beijing and Shanghai exceeded 50 Mg·grid-1. In contrast, IVOC emissions over western China were relatively lower, with a network structure gathering around the traffic arteries serving inter-provincial transportation. This study underscored the importance of having a localized emission factor to better reflect the IVOC emission characteristics from Chinese vehicles and to improve the assessment of their environmental impacts.

Characterizing the particle number emissions of light-duty gasoline vehicles under different engine technologies and driving conditions.

Vehicle particle number (PN) emissions have attracted increasing public attention due to their severe influence on human health. In this study, we selected 35 light-duty gasoline vehicles (LDGVs) with gasoline direct injection (GDI) and multi-port fuel injection (MPFI) engines to elucidate the main factors influencing PN emissions. Via real driving emission (RDE) and chassis dynamometer tests, we quantified the impact of engine technology, emission standards, engine-start conditions and engine load on vehicle PN emissions. The RDE test results indicated that GDI vehicles generated higher PN emissions than those of MPFI vehicles under hot-running conditions. MPFI vehicle PN emissions were greatly affected by rapidly changing driving conditions, especially vehicles equipped with automatic start-stop systems. In regard to China 6 GDI vehicles equipped with a gasoline particle filter (GPF), their PN emissions were usually low, and peak PN emissions could mainly be attributed to GPF regeneration. Engine manufacturers should optimize GPF regeneration conditions to further reduce particulate emissions. Furthermore, the analysis results of PN emissions for different road types indicated that PN emissions were related to vehicle driving conditions. The vehicle specific power (VSP) could be used as an important explanatory variable to characterize the PN emission rate when distinguishing different engine technologies and emission standards. A real-world LDGV VSP-based PN emission rate was suggested based on the RDE test dataset. The VSP-based emission rate could be considered to more accurately quantify vehicle PN emissions and support the formulation of urban vehicle particle emission control policies.

Environmental Controls to Soil Heavy Metal Pollution Vary at Multiple Scales in a Highly Urbanizing Region in Southern China.

Natural and anthropogenic activities affect soil heavy metal pollution at different spatial scales. Quantifying the spatial variability of soil pollution and its driving forces at different scales is essential for pollution mitigation opportunities. This study applied a multivariate factorial kriging technique to investigate the spatial variability of soil heavy metal pollution and its relationship with environmental factors at multiple scales in a highly urbanized area of Guangzhou, South China. We collected 318 topsoil samples and used five types of environmental factors for the attribution analysis. By factorial kriging, we decomposed the total variance of soil pollution into a nugget effect, a short-range (3 km) variance and a long-range (12 km) variance. The distribution of patches with a high soil pollution level was scattered in the eastern and northwestern parts of the study domain at a short-range scale, while they were more clustered at a long-range scale. The correlations between the soil pollution and environmental factors were either enhanced or counteracted across the three distinct scales. The predictors of soil heavy metal pollution changed from the soil physiochemical properties to anthropogenic dominated factors with the studied scale increase. Our study results suggest that the soil physiochemical properties were a good proxy to soil pollution across the scales. Improving the soil physiochemical properties such as increasing the soil organic matter is essentially effective across scales while restoring vegetation around pollutant sources as a nature-based solution at a large scale would be beneficial for alleviating local soil pollution.

Upgrading Emission Standards Inadvertently Increased OH Reactivity from Light-Duty Diesel Truck Exhaust in China: Evidence from Direct LP-LIF Measurement.

Vehicular exhaust is an important source of reactive gases responsible for the formation of ozone and secondary organic aerosols (SOAs) in the atmosphere. Although significant efforts have been made to characterize the chemical compounds associated with vehicular exhaust, there is still a wealth of compounds that are unable to be detected, posing uncertainties in estimating their contribution to atmospheric reactivity. In this study, by improving laser-induced fluorescence techniques, we achieved the first-ever direct measurement of the total OH reactivity (TOR) from light-duty diesel truck (LDDT) exhaust with different emission standards. We found that the TOR from the LDDT exhaust was 80-130 times the TOR from the gasoline exhaust measured in Japan. Unexpectedly, we discovered increased TOR emissions along with upgrading emission standards, possibly as a collective result of high combustion temperature in the engine and the oxidation catalysts in the exhaust after-treatment that favor production of highly oxidized organics in the stricter emission standard. Most of these oxidized organics are unable to be speciated by routine measurements, resulting in the missing OH reactivity increasing rapidly from 1.91% for China III to 42.0% for China V LDDT. Upgrading the emission standard failed to reduce the TOR from LDDT exhaust, which may inadvertently promote the contribution of LDDT to the formation of ozone and SOA pollution in China.

A meteorologically adjusted ensemble Kalman filter approach for inversing daily emissions: A case study in the Pearl River Delta, China.

The conventional Ensemble Kalman filter (EnKF), which is now widely used to calibrate emission inventories and to improve air quality simulations, is susceptible to simulation errors of meteorological inputs, making accurate updates of high temporal-resolution emission inventories challenging. In this study, we developed a novel meteorologically adjusted inversion method (MAEInv) based on the EnKF to improve daily emission estimations. The new method combines sensitivity analysis and bias correction to alleviate the inversion biases caused by errors of meteorological inputs. For demonstration, we used the MAEInv to inverse daily carbon monoxide (CO) emissions in the Pearl River Delta (PRD) region, China. In the case study, 60% of the total CO simulation biases were associated with sensitive meteorological inputs, which would lead to the overestimation of daily variations of posterior emissions. Using the new inversion method, daily variations of emissions shrank dramatically, with the percentage change decreased by 30%. Also, the total amount of posterior CO emissions estimated by the MAEInv decreased by 14%, indicating that posterior CO emissions might be overestimated using the conventional EnKF. Model evaluations using independent observations revealed that daily CO emissions estimated by MAEInv better reproduce the magnitude and temporal patterns of ambient CO concentration, with a higher correlation coefficient (R, +37.0%) and lower normalized mean bias (NMB, -17.9%). Since errors of meteorological inputs are major sources of simulation biases for both low-reactive and reactive pollutants, the MAEInv is also applicable to improve the daily emission inversions of reactive pollutants.

[Volatile Organic Compound Emission Characteristics and Influences Assessment of a Petrochemical Industrial Park in the Pearl River Delta Region].

The petrochemical industry is one of the major emission sources of volatile organic compounds (VOCs). However, the current studies have mostly focused on the identification of the chemical characteristics of non-methane hydrocarbon (NMHC) VOCs species from the petroleum refining sub-sector. Research on the characteristics of VOCs components in oxygenated VOCs (OVOCs) species and other important sub-sectors is still lacking. Therefore, eight enterprises at a petrochemical industrial park in the Pearl River Delta region were carefully selected to represent three major subsectors, namely petroleum refining, synthetic materials, and organic chemicals, for the petrochemical industry. The VOCs (including 22 OVOCs species) from stack emissions and fugitive emissions, as well as nearby sensitive sites, were sampled, and the source reactivity (SR), the thresholds of malodor, and the carcinogenic and non-carcinogenic risks were assessed. The main results were as follows:① the VOCs concentrations of the stack emissions from the petrochemical industrial park were between 0.2-46.3 mg·m-3. The VOCs species were greatly affected by the type of after-treatment technology. A major VOC species emitted from the combustion-based after treatments was formaldehyde, whereas the species emitted from the non-combustion-based equipment were acetone, 1,3-butadiene, acrylic, and isobutane. ② The fugitive VOCs emissions from the petroleum storage tank area were dominated by alkanes, whereas the other fugitive emission sites and the sensitive sites were dominated by OVOCs such as acetone, formaldehyde, and ethyl acetate. ③ The SRs were mainly contributed by OVOCs, aromatics, and olefins, with average proportions of 43.1%, 24.2%, and 21.1%, respectively, with the major species being formaldehyde, acetaldehyde, m/p-xylene, ethylene, and toluene. ④ The malodor appeared both in fugitive emission areas and the sensitive sites. The main odor components were OVOCs such as n-butyraldehyde, propionaldehyde, hexanal, and valeraldehyde. ⑤ The non-carcinogenic risks occurred in the fugitive emission areas and the sensitive sites of resin, alcohol, and aldehyde production, which were mainly caused by OVOCs such as free acetaldehyde, acrolein, and propionaldehyde. No carcinogenic risk was found in any of the sampled sites. This research can provide scientific support for the formulation of priority VOCs species-based precise control strategies in petrochemical industrial parks.

A newly integrated dataset of volatile organic compounds (VOCs) source profiles and implications for the future development of VOCs profiles in China.

Volatile organic compounds (VOCs) source profiles can be used for a number of purposes, such as creating speciated air pollutant emission inventories and providing inputs to receptor and air quality models. In this study, we first collected and schematically evaluated more than 500 Chinese domestic source profiles from literature and field measurements, and then established a most up-to-date dataset of VOCs source profiles in China by integrating 363 selective VOCs profiles into 101 sector-based source profiles. The profile dataset covers eight major source categories and contains 447 VOCs species including non-methane hydrocarbons (NMHCs) species and oxygenated VOCs (OVOCs) species. The results shown that (1) VOCs composition characteristics exhibit variations for most Level-II source sectors and Level-III sub-sectors even under the same Level-I source category; (2) OVOCs, which were significantly missing in previous profiles, account for more than 95% in cooking and 20- 40% in non-road mobile, biomass burning and solvent use sources; (3) aromatics account for 20%-40% in most emission sources except cooking source, alkenes and alkynes account for ~20% in combustion sources (stationary combustion, mobile source and biomass burning), alkanes are abundant in gasoline-related emission sources(on-road mobile source and fuel oil storage and transportation); (4) missing OVOCs species could bring 30%-50% to ozone formation potentials in most emission sources; and (5) there are considerable differences in VOCs chemical groups and individual species for most emission sources between this dataset and the widely used U.S. SPECIATE database, indicating the importance of developing domestic VOCs source profiles. The dataset developed in this study can help support reactive VOCs species-based ozone control strategy and provide domestic profile data for source apportionment and air quality modeling in China and other countries or regions with similar emission source characteristics.

Variability in real-world emissions and fuel consumption by diesel construction vehicles and policy implications.

Strategically reducing the emission of non-road mobile source especially diesel construction vehicle (DCV) has a large potential in improving air quality and has attracted much scientific and public attention in recent years around the world. In this study, we explored real-world fuel consumption rate and gaseous emissions factors for multiple pollutants of three typical DCVs in China. The sampling campaign considered the operation mode, cumulative operation hour, emission standard stage and engine power. Results show that the accumulated fuel consumption per hour of vehicle weight for working, load-free moving and idling modes was 0.3, 0.2 and 0.1 kg/h·tons, respectively. The fuel-based NOx emission factor exhibited a bimodal distribution at 27 and 41 g/kg. The fuel-based emission factors for volatile organic compounds (VOCs) were in the range of 0.8 to 2.6 g/kg, where alkene and alkane were the dominant components (>80%), i.e., ethylene, acetylene, propylene, and isobutane. We observed that the ratio of toluene and benzene concentration (T/B) (1.4 ± 1.3) differed from other key emission sources and may be used as the specific indicator of DCV emission exhaust. Our estimates suggest that in 2017 the fuel consumption and NOx emissions of DCV emission accounted for 22-28% of non-road mobile sources in China; NOX emissions were 2.7 times higher than those in 2006, and it is forecasted that NOx emissions would reduce by 23% between 2017 and 2025 with the implementation of stage IV and the strict supervision policy. The comprehensive dataset on DCV emissions will either guide the government to establish precise and effective policies to regulate the non-road mobile source or significantly improve our understanding of source apportionment of atmospheric NOx and VOCs, both of which are key precursors of haze and ozone pollution.

Identification of two main origins of intermediate-volatility organic compound emissions from vehicles in China through two-phase simultaneous characterization.

Intermediate-volatility organic compounds (IVOCs) emitted from vehicles are generally in the gas phase but may partly partition into particle phase when measured under ambient temperature. To have a complete and accurate picture of IVOC emissions from vehicles, gas- and particle-phase IVOCs from a fleet of gasoline and diesel vehicles were simultaneously characterized by dynamometer testing in Guangzhou, China. The total IVOC emission factors of the diesel vehicles were approximately 16 times those of the gasoline vehicles, and IVOCs were mainly concentrated in the particle phase in the form of the unresolved complex mixture (UCM). The chemical compositions and volatility distributions of the gas-phase IVOCs differed much between gasoline and diesel vehicles, but were similar to those of their respective fuel content. This indicated that vehicle fuel is the main origin for the gas-phase IVOC emissions from vehicles. In comparison, the chemical compositions of the particle-phase IVOCs from gasoline and diesel vehicles were similar and close to lubricating oil content, implying that lubricating oil plays an important role in contributing to particle-phase IVOCs. The highest IVOC fraction in the particle phase occurred from B16-B18 volatility bins, overall accounting for more than half of the particle-phase IVOCs for both the gasoline and diesel vehicles. A conceptual model was developed to articulate the distributions of lubricating oil contents and their evaporation and nucleation/adsorption capabilities in the different volatility bins. The IVOCs-produced secondary organic aerosol (SOA) were 1.4-2.6 and 3.9-11.7 times POAs emitted from the gasoline and diesel vehicles, respectively. The tightening of emission standards had not effectively reduced IVOC emissions and the SOA production until the implementation of China VI emission standard. This underscores the importance of accelerating the promotion of the latest emission standard to alleviate pollution from vehicles in China.

An updated model-ready emission inventory for Guangdong Province by incorporating big data and mapping onto multiple chemical mechanisms.

An accurate characterization of spatial-temporal emission patterns and speciation of volatile organic compounds (VOCs) for multiple chemical mechanisms is important to improving the air quality ensemble modeling. In this study, we developed a 2017-based high-resolution (3 km × 3 km) model-ready emission inventory for Guangdong Province (GD) by updating estimation methods, emission factors, activity data, and allocation profiles. In particular, a full-localized speciation profile dataset mapped to five chemical mechanisms was developed to promote the determination of VOC speciation, and two dynamic approaches based on big data were used to improve the estimation of ship emissions and open fire biomass burning (OFBB). Compared with previous emissions, more VOC emissions were classified as oxygenated volatile organic compound (OVOC) species, and their contributions to the total ozone formation potential (OFP) in the Pearl River Delta (PRD) region increased by 17%. Formaldehyde became the largest OFP species in GD, accounting for 11.6% of the total OFP, indicating that the model-ready emission inventory developed in this study is more reactive. The high spatial-temporal variability of ship sources and OFBB, which were previously underestimated, was also captured by using big data. Ship emissions during typhoon days and holidays decreased by 23-55%. 95% of OFBB emissions were concentrated in 9% of the GD area and 31% of the days in 2017, demonstrating their strong spatial-temporal variability. In addition, this study revealed that GD emissions have changed rapidly in recent years due to the leap-forward control measures implemented, and thus, they needed to be updated regularly. All of these updates led to a 5-17% decrease in the emission uncertainty for most pollutants. The results of this study provide a reference for how to reduce uncertainties in developing model-ready emission inventories.

High Gaseous Nitrous Acid (HONO) Emissions from Light-Duty Diesel Vehicles.

Nitrous acid (HONO) plays an important role in the budget of hydroxyl radical (•OH) in the atmosphere. Vehicular emissions are a crucial primary source of atmospheric HONO, yet remain poorly investigated, especially for diesel trucks. In this study, we developed a novel portable online vehicular HONO exhaust measurement system featuring an innovative dilution technique. Using this system coupled with a chassis dynamometer, we for the first time investigated the HONO emission characteristics of 17 light-duty diesel trucks (LDDTs) and 16 light-duty gasoline vehicles in China. Emissions of HONO from LDDTs were found to be significantly higher than previous studies and gasoline vehicles tested in this study. The HONO emission factors of LDDTs decrease significantly with stringent control standards: 1.85 ± 1.17, 0.59 ± 0.25, and 0.15 ± 0.14 g/kg for China III, China IV, and China V, respectively. In addition, we found poor correlations between HONO and NOx emissions, which indicate that using the ratio of HONO to NOx emissions to infer HONO emissions might lead to high uncertainty of HONO source budget in previous studies. Lastly, the HONO emissions are found to be influenced by driving conditions, highlighting the importance of conducting on-road measurements of HONO emissions under real-world driving conditions. More direct measurements of the HONO emissions are needed to improve the understanding of the HONO emissions from mobile and other primary sources.