Contribution of Vehicle Emission and NO2 Surface Conversion to Nitrous Acid (HONO) in Urban Environments: Implications from Tests in a Tunnel.

Nitrous acid (HONO) is an important photochemical precursor to hydroxyl radicals particularly in an urban atmosphere, yet its primary emission and secondary production are often poorly constrained. Here, we measured HONO and nitrogen oxides (NOx) at both the inlet and the outlet in a busy urban tunnel (>30 000 vehicles per day) in south China. Multiple linear regression revealed that 73.9% of the inlet-outlet incremental HONO concentration was explained by NO2 surface conversion, while the rest was directly emitted from vehicles with an average HONO/NOx ratio of 1.31 ± 0.87%, which was higher than that from previous tunnel studies. The uptake coefficient of NO2, γ(NO2), on the tunnel surfaces was calculated to be (7.01 ± 0.02) × 10-5, much higher than that widely used in models. As tunnel surfaces are typical of urban surfaces in the wall and road materials, the dominance of HONO from surface reactions in the poorly lit urban tunnel demonstrated the importance of NO2 conversion on urban surfaces, instead of NO2 conversion on the aerosol surface, for both daytime and night-time HONO even in polluted ambient air. The higher γ(NO2) on urban surfaces and the elevated HONO/NOx ratio from this study can help explain the missing HONO sources in urban areas.

Emissions and light absorption of carbonaceous aerosols from on-road vehicles in an urban tunnel in south China.

With changing numbers, compositions, emission standards and fuel quality of on-road vehicles, it is imperative to accordingly characterize and update vehicular emissions of carbonaceous aerosols for better understanding their health and climatic effects. In this study, a 7-day field campaign was conducted in 2019 in a busy urban tunnel (>30,000 vehicles day-1) in south China with filter-based aerosol samples collected every 2 h at both the inlet and the outlet for measuring carbonaceous aerosols and their light absorbing properties. Observed fleet average emission factor (EF) of total carbon (TC) was 13.4 ± 8.3 mg veh-1 km-1, and 17.4 ± 11.3 mg veh-1 km-1 if electric and LPG-driven vehicles were excluded; and fleet average EF of organic carbon (OC) and elemental carbon (EC) was 8.5 ± 6.6 and 4.9 ± 2.6 mg veh-1 km-1 (11.0 ± 8.8 and 6.3 ± 3.6 mg veh-1 km-1 if excluding electric and LPG vehicles), respectively. Regression analysis revealed an average TC-EF of 319.8 mg veh-1 km-1 for diesel vehicles and 2.1 mg veh-1 km-1 for gasoline vehicles, and although diesel vehicles only shared ~4% in the fleet compositions, they still dominate on-road vehicular carbonaceous aerosol emissions due to their over 150 times higher average TC-EF than gasoline vehicles. Filter-based light absorption measurement demonstrated that on average brown carbon (BrC) could account for 19.1% of the total carbonaceous light absorption at 405 nm, and the average mass absorption efficiency of EC at 635 nm and that of OC at 405 nm were 5.2 m2 g-1 C and 1.0 m2 g-1 C, respectively.

Emission factors of ammonia for on-road vehicles in urban areas from a tunnel study in south China with laser-absorption based measurements.

Vehicle emission is an important source of ammonia (NH3) in urban areas. To better address the role of vehicle emission in urban NH3 sources, the emission factor of NH3 (NH3-EF) from vehicles running on roads under real-world conditions (on-road vehicles) needs to update accordingly with the increasingly tightened vehicle emission standards. In this study, laser-absorption based measurements of NH3 were conducted during a six-day campaign in 2019 at a busy urban tunnel with a daily traffic flow of nearly 40,000 vehicles in south China's Pearl River Delta (PRD) region. The NH3-EF was measured to be 16.6 ± 6.3 mg km-1 for the on-road vehicle fleets and 19.0 ± 7.2 mg km-1 for non-electric vehicles, with an NH3 to CO2 ratio of 0.27 ± 0.09 ppbv ppmv-1. Multiple linear regression revealed that the average NH3-EFs for gasoline vehicles (GVs), liquefied petroleum gas vehicles, and heavy-duty diesel vehicles (HDVs) were 18.8, 15.6, and 44.2 mg km-1, respectively. While NH3 emissions from GVs were greatly reduced with enhanced performance of engines and catalytic devices to meet stricter emission standards, the application of urea selective catalytic reduction (SCR) in HDVs makes their NH3 emission an emerging concern. Based on results from this study, HDVs may contribute over 11% of the vehicular NH3 emissions, although they only share ∼4% by vehicle numbers in China. With the updated NH3-EFs, NH3 emission from on-road vehicles was estimated to be 9 Gg yr-1 in the PRD region in 2019, contributing only 5% of total NH3 emissions in the region, but still might be a dominant NH3 source in the urban centers with little agricultural activity.

Evaluating the effectiveness of multiple emission control measures on reducing volatile organic compounds in ambient air based on observational data: A case study during the 2010 Guangzhou Asian Games.

Volatile organic compounds (VOCs) play a crucial role in modulating air pollution by ozone and fine particles, particularly in urban areas. While in recent years short-term intervention actions for better air quality during big events in China did present good opportunities to examine the effectiveness of control measures in reducing anthropogenic VOCs emission, it is highly challenging to interpret the real effect of a specific control measure based on field monitoring data when a cocktail of control measures were adopted. Here we took the air quality intervention actions during the 16th Asian Games (AG) in Guangzhou as a case study to explore the impact of short-term multiple measures on VOCs reduction. The average mass concentrations of VOCs decreased by 52-68% during the AG. These percentages could not reflect emission reduction rates as the concentration might be also heavily impacted by dispersion conditions. Diagnostic ratios, such as methyl tert-butyl ether to carbon monoxide (MTBE/CO) and i-pentane/CO, decreased by over 60% during the AG, suggesting a substantial reduction in gasoline related emissions. A method linking emission reduction rates of two sources with their contribution percentages before and during the AG by using a receptor model was further formulated. With the available reduction rate of 34% for vehicular exhaust obtained during the traffic restriction drill in our previous study, VOCs emissions from gasoline evaporation and solvent use reduced by 45.7% and 13.6% during the AG, respectively. Total VOCs emissions decreased by 25.3% on average during the AG, and the emission control of vehicular exhaust, oil evaporation, and solvent use accounted for 17.0%, 6.3% and 2.0% of total VOCs emission reduction, respectively. This study presented an observed-based method with diagnostic/quantitative approaches to single out the effectiveness of each control measures in reducing VOCs emissions.

Decadal changes in emissions of volatile organic compounds (VOCs) from on-road vehicles with intensified automobile pollution control: Case study in a busy urban tunnel in south China.

In the efforts at controlling automobile emissions, it is important to know in what extent air pollutants from on-road vehicles could be truly reduced. In 2014 we conducted tests in a heavily trafficked tunnel in south China to characterize emissions of volatile organic compounds (VOC) from on-road vehicle fleet and compared our results with those obtained in the same tunnel in 2004. Alkanes, aromatics, and alkenes had average emission factors (EFs) of 338, 63, and 42 mg km-1 in 2014 against that of 194, 129, and 160 mg km-1 in 2004, respectively. In 2014, LPG-related propane, n-butane and i-butane were the top three non-methane hydrocarbons (NMHCs) with EFs of 184 ± 21, 53 ± 6 and 31 ± 3 mg km-1; the gasoline evaporation marker i-pentane had an average EF of 17 ± 3 mg km-1; ethylene and propene were the top two alkenes with average EFs of 16 ± 1 and 9.7 ± 0.9 mg km-1, respectively; isoprene had no direct emission from vehicles; toluene showed the highest EF of 11 ± 2 mg km-1 among the aromatics; and acetylene had an average EF of 7 ± 1 mg km-1. While EFs of total NMHCs decreased only 9% from 493 ± 120 mg km-1 in 2004 to 449 ± 40 mg km-1 in 2014, their total ozone formation potential (OFP) decreased by 57% from 2.50 × 103 mg km-1 in 2004 to 1.10 × 103 mg km-1 in 2014, and their total secondary organic aerosol formation potential (SOAFP) decreased by 50% from 50 mg km-1 in 2004 to 25 mg km-1 in 2014. The large drop in ozone and SOA formation potentials could be explained by reduced emissions of reactive alkenes and aromatics, due largely to fuel transition from gasoline/diesel to LPG for taxis/buses and upgraded vehicle emission standards.

[Emission Factors and Preliminary Emission Estimates of Air Pollutants from Ships at Berth in the Guangzhou Port].

Three large container vessels over a tonnage of 40×103 t at berth in the Guangzhou Port were selected for determination of air pollutants in exhausts from auxiliary engines to obtain fuel-based emission factors (EFs). The fuel-based EFs for vessels A, B, and C at berth were 3096, 3031, and 3028 g·kg-1, respectively, for CO2; 61.8, 19.9, and 27.0 g·kg-1 for NOx; 8.0, 4.0, and 5.3 g·kg-1 for CO; 31.4, 41.9, and 56.7 g·kg-1 for SO2; 2.4, 1.1, and 1.5 g·kg-1 for PM2.5; and 0.13, 0.09, and 0.17 g·kg-1 for VOCs. With the basic information about ship types, arrival times, and berthing times, the emissions of NOx, CO, SO2, PM2.5, and NH3 from a ship at berth in the Guangzhou Port in 2014 were roughly estimated to be 1231, 226, 1229, 47.6 and 0.04 t, respectively, with ships with a tonnage of 10×103-50×103 t sharing the largest burdens, followed by ships over a tonnage of 50×103 t. Estimated emission of VOCs from ships at berth in the Guangzhou Port was about 33.6 t, with vessels below a tonnage of 3×103 t contributing the most.

[BTX monitoring nearby main road traffic in Guangzhou].

In order to study the levels of BTX (benzene, toluene, xylene, etc) nearby the main roads of Guangzhou from November 2010 to December 2010 during the Asian Games, BTX and conventional pollutants such as NO2, O3 in the air were monitored by the DOAS system nearby Huangsha Road, which is in the Liwan District of Guangzhou City. The results showed that, during the entire period, BTX showed a high concentration in the evening and the average concentrations of benzene, toluene, p-xylene, m-xylene and phenol were 15.9 microg x m(-3), 61.3 microg x m(-3), 6.5 microg x m(-3), 16.9 microg x m(-3), 0.88 microg x m(-3), respectively. The average concentrations of benzene and toluene were close to those in other cities, and the ratio of toluene to benzene was in range of 1.2-6.16. Throughout the monitoring period, the correlation coefficient of benzene and toluene was 0.86 and it rose to 0.985 during the high concentration period, indicating that they had the same source in this region. The correlation coefficient between toluene and CO was 0.78, indicating that traffic emissions was the major source of benzene and toluene. Based on the combination of wind speed, wind direction and other meteorological data, it was found that the weather condition was an important factor which affected the BTX concentration, and some possible point sources were suggested nearby the site.