Application of roadside air purifiers in urban street canyons: A pilot-scale study in Hong Kong.

The implementation of roadside air purifiers has emerged as an effective active control measure to alleviate air pollution in urban street canyons. However, technical questions raised under real conditions remain challenging. In this study, we conducted a pilot-scale investigation involving seven units of self-designed roadside air purifiers in an urban street canyon in Hong Kong. The air cleaning effects were quantified with an air quality sensor network after rigorous quality control. The removal efficiencies of Nitrogen dioxide (NO2), Fine suspended particulates (PM2.5), Carbon monoxide (CO), and Nitric oxide (NO) were determined by comparing with simultaneously measured ambient concentrations, with hourly average efficiencies of 14.0 %-16.9 %, 3.5-10.0 %, 11.9 %-18.7 %, and 19.2 %-44.9 %, respectively. Generally, the purification effects presented variations depending on the ambient pollutants' levels. Higher ambient concentrations of NO2, PM2.5, CO correlated with increased purification effects, while NO presented the opposite trend. The influence of interval distance combined with spatial distribution indicated the operation of purifiers will induce local NO2 attenuation even at an interval distance of four meters. Statistical analysis delivered evidence the air cleaning ability exhibited optimal performance when relative humidity level is ranged from 70 % to 90 %, aligning with the prevailing conditions in Hong Kong. Additionally, improved purification effects were observed at the downwind direction, and their performance was enhanced when the wind speed exceeded 2.5 m/s. Moreover, we estimated the operational lifetime of the air purifiers to be approximately 130 days, offering crucial information regarding the filter replacement cycle. This work serves as a pioneering case study, showcasing the feasibility and deployment considerations of roadside air purifiers in effectively controlling air pollution in urban environments.

Comprehensive Assessment of Pollution Sources and Health Impacts in Suburban Area of Shanghai.

Shanghai, one of China's largest metropolises, faces significant environmental pollution challenges due to rapid economic development. Suburban areas of Shanghai are affected by both long-distance transport and local sources of pollutants. This study conducted an integrated analysis that links health-risk assessment of heavy metals and source apportionment of atmospheric constituents to distinguish the contributions of emission sources and the major sources of health risks. Source-apportionment analysis revealed that secondary sources had the greatest contribution to the local pollutants, indicating the significant influence of peripheral and long-distance transport. Health-risk assessment of Cr, Ni, As, and Cd revealed that local residents were exposed to respiratory health risks, in which Cr is the major contributor. This health risk was primarily associated with emissions from nearby industry-related sources. Our study highlights the significant effects of both long-distance transport and local source emissions on atmospheric composition and human health in large urban agglomerations. The findings can inform future efforts to develop more precise emission-reduction strategies and policy improvements to mitigate environmental pollution and protect public health.

Exposure and health risk assessment of PM2.5-bound polycyclic aromatic hydrocarbons during winter at residential homes: A case study in four Chinese cities.

Residential indoor PM2.5 were concurrently collected in Hong Kong, Guangzhou, Shanghai, and Xi'an during the winter and early spring seasons of 2016-2017, for updating the current knowledge of the spatial variation of indoor air pollution and the potential health risks in China. PM2.5-bound polycyclic aromatic hydrocarbons (PAHs) were characterized, and the associated inhalation cancer risks were assessed by a probabilistic approach. Higher levels of indoor PAHs were identified in Xi'an residences (averaged at 176.27 ng m-3) with those of other cities ranging from 3.07 to 15.85 ng m-3. Traffic-related fuel combustion was identified as a common contributor to indoor PAHs through outdoor infiltration for all investigated cities. Indoor PAHs profiles showed city-specific differences, while distinctions between profiles based on indoor activities or ambient air quality were limited. Similar with the total PAHs concentrations, the estimated toxic equivalencies (TEQ) with reference to benzo[a]pyrene in Xi'an residences (median at 18.05 ng m-3) were above the recommended value of 1 ng m-3 and were magnitudes higher than the other investigated cities with estimated median TEQ ranging from 0.27 to 1.55 ng m-3. Incremental lifetime cancer risk (ILCR) due to PAHs inhalation exposure was identified with a descending order of adult (median at 8.42 × 10-8) > adolescent (2.77 × 10-8) > children (2.20 × 10-8) > senior (1.72 × 10-8) for different age groups. Considering the lifetime exposure-associated cancer risk (LCR), potential risks were identified for residents in Xi'an as an LCR level over 1 × 10-6 was identified for half of the adolescent group (median at 8.96 × 10-7), and exceedances were identified for about 90 % of the groups of adults (10th percentile at 8.29 × 10-7) and seniors (10th percentile at 1.02 × 10-6). The associated LCR estimated for other cities were relatively insignificant.

Volatile organic compounds at a roadside site in Hong Kong: Characteristics, chemical reactivity, and health risk assessment.

Volatile organic compounds (VOCs) and oxygenated VOCs (OVOCs) play important roles in atmospheric chemistry and are recognized as the major pollutants in roadside microenvironments of metropolitan Hong Kong, China. In this study, the ambient VOCs and OVOCs were intensively monitored at a roadside site in Hong Kong for one month during morning and evening rush hours. The emission characterizations, as well as ozone formation potentials (OFP) and hydroxyl radical (OH) loss rates (LOH) were determined. Results from the campaign showed that the average concentrations of detected VOCs/OVOCs ranged from 0.21 to 9.67 ppb, and higher toluene to benzene (T/B) ratio was observed during evening sections due to the variation of fuel types in vehicle fleets and mix of additional emission sources in this site. On average, OVOCs had much higher concentrations than the targeted VOC species. Acetone, formaldehyde, and acetaldehyde were the three most abundant species, while formaldehyde showed the highest contributions to both OFP (32.20 %) and LOH (16.80 %). Furthermore, potential health hazards with inhalation exposure to formaldehyde, acetaldehyde, propionaldehyde, methyl ethyl ketone (MEK), 1,3-butadiene, toluene, benzene, and acrylonitrile were found. These results reveal that it is imperative to implement efficient control measures to reduce vehicle emissions for both primary and secondary pollutants and to protect both roadside workers and pedestrians.

Long-term variation and evaluation of air quality across Hong Kong.

Study of Air Quality Objectives (AQOs) and long-term changes of air pollution plays a decisive role in formulating and refining pollution control strategies. In this study, 10-year variations of six major air pollutants were analyzed at seven monitoring sites in Hong Kong. The continuous decrease of annual averaged concentrations of NO2, SO2, CO, PM2.5 and PM10 and numbers of days with severe pollution conditions validated the efficiency of the series of air pollution control schemes implemented by the Hong Kong government. However, there is still a big gap to meet the ultimate targets described by the World Health Organization. Besides, the concentration of O3 at roadside and urban stations increased by 135% ± 25% and 37% ± 18% from 2011 to 2020, respectively, meanwhile the highest 8 hr averaged O3 concentration was observed as 294 µg/m3 at background station in 2020, which pointed out the increasing ozone pollution in Hong Kong. There was a great decrease in the annual times of air quality health index (AQHI) laying in "high", "very high" and "serious" categories from 2011 to 2020 with the decrease rate of 89.70%, 91.30% and 89.74% at roadside stations, and 79.03%, 95.98% and 72.73% at urban stations, respectively. Nevertheless, the number of days categorized as "high" or above at roadside station was twice more than that in the urban station during the past ten years. Thus, more policies and attentions should be given to the roadside air quality and its adverse health effect to pedestrians on street.

Increased contribution to PM2.5 from traffic-influenced road dust in Shanghai over recent years and predictable future.

Traffic contributes to fine particulate matter (PM2.5) in the atmosphere through engine exhaust emissions and road dust generation. However, the evolution of traffic related PM2.5 emission over recent years remains unclear, especially when various efforts to reduce emission e.g., aftertreatment technologies and high emission standards from China IV to China V, have been implemented. In this study, hourly elemental carbon (EC), a marker of primary engine exhaust emissions, and trace element of calcium (Ca), a marker of road dust, were measured at a nearby highway sampling site in Shanghai from 2016 to 2019. A random forest-based machine learning algorithm was applied to decouple the influences of meteorological variables on the measured EC and Ca, revealing the deweathered trend in exhaust emissions and road dust. After meteorological normalization, we showed that non-exhaust emissions, i.e., road dust from traffic, increased their fractional contribution to PM2.5 over recent years. In particular, road dust was found to be more important, as revealed by the deweathered trend of Ca fraction in PM2.5, increasing at 6.1% year-1, more than twice that of EC (2.9% year-1). This study suggests that while various efforts have been successful in reducing vehicular exhaust emissions, road dust will not abate at a similar rate. The results of this study provide insights into the trend of traffic-related emissions over recent years based on high temporal resolution monitoring data, with important implications for policymaking.

Slower than expected reduction in annual PM2.5 in Xi'an revealed by machine learning-based meteorological normalization.

To evaluate the effectiveness of air pollution control policies, trend analysis of the air pollutants is often performed. However, trend analysis of air pollutants over multiple years is complicated by the fact that changes in meteorology over time can also affect the levels of air pollutants in addition to changes in emissions or atmospheric chemistry. To decouple the meteorological effect, this study performed a trend analysis of the hourly fine particulate matter (PM2.5) observed at an urban background site in Xi'an city over 5 years from 2015 to 2019 using the machine learning algorithm. As a novel way of meteorological normalization, the meteorological parameters were used as constant input for 5 consecutive years. In this way, the impact of meteorological parameters was excluded, providing insights into the "real" changes in PM2.5 due to changes in emission strength or atmospheric chemistry. After meteorological normalization, a decreasing trend of -3.3 % year-1 (-1.9 µg m-3 year-1) in PM2.5 was seen, instead of -4.4 % year-1 from direct PM2.5 observation. Assuming the rate of -1.9 µg m-3 year-1 were kept constant for the next few decades in Xi'an, it would take approximately 25 years (in the year 2045) to reduce the annual PM2.5 level to 5 µg m-3, the new guideline value from World Health Organization. We also show that PM2.5 is primarily associated with anthropogenic emissions, which, underwent aqueous phase chemistry in winter and photochemical oxidation in summer as suggested by partial dependence of RH and Ox in different seasons. Therefore, reducing the anthropogenic secondary aerosol precursors at a higher rate, such as NOx and VOCs is expected to reduce the particulate pollution in this region more effectively than the current -3.3 % year-1 found in this study.

Metal-Organic Frameworks for NOx Adsorption and Their Applications in Separation, Sensing, Catalysis, and Biology.

Nitrogen oxide (NOx ) is a family of poisonous and highly reactive gases formed when fuel is burned at high temperatures during anthropogenic behavior. It is a strong oxidizing agent that significantly contributes to the ozone and smog in the atmosphere. Thus, NOx removal is important for the ecological environment upon which the civilization depends. In recent decades, metal-organic frameworks (MOFs) have been regarded as ideal candidates to address these issues because they form a reticular structure between proper inorganic and organic constituents with ultrahigh porosity and high internal surface area. These characteristics render them chemically adaptable for NOx adsorption, separation, sensing, and catalysis. In additional, MOFs enable potential nitric oxide (NO) delivery for the signaling of molecular NO in the human body. Herein, the different advantages of MOFs for coping with current environmental burdens and improving the habitable environment of humans on the basis of NOx adsorption are reviewed.

FeCo alloy encased in nitrogen-doped carbon for efficient formaldehyde removal: Preparation, electronic structure, and d-band center tailoring.

Formaldehyde is a typical indoor air pollutant that has posed severely adverse effects on human health. Herein, a novel FeCo alloy nanoparticle-embedded nitrogen-doped carbon (FeCo@NC) was synthesized with the aim of tailoring the transition-metal d-band structure toward an improved formaldehyde oxidation activity for the first time. A unique core@shell metal-organic frameworks (MOFs) architecture with a Fe-based Prussian blue analogue core and Co-containing zeolite imidazole framework shell was firstly fabricated. Then, Fe and Co ion alloying was readily achieved owing to the inherent MOF porosity and interionic nonequilibrium diffusion occurring during pyrolysis. High-angle annular dark-field scanning transmission electron microscopy and X-ray absorption fine structure spectra confirm that small FeCo alloys in situ form in FeCo@NC, which exhibits a higher formaldehyde removal efficiency (93%) than the monometallic Fe-based catalyst and a remarkable CO2 selectivity (85%) at room temperature. Density functional theory calculations indicate the number of electrons transferred from the metal core to the outer carbon layer is altered by alloying Fe and Co. More importantly, a downshift in the d-band center relative to the Fermi level occurs from - 0.93 to - 1.04 eV after introducing Co, which could alleviate the adsorption of reaction intermediates and greatly improve the catalytic performance.

Exploring the photocatalytic conversion mechanism of gaseous formaldehyde degradation on TiO2-x-OV surface.

To understand the conversion mechanism of photocatalytic gaseous formaldehyde (HCHO) degradation, strontium (Sr)-doped TiO2-x-OV catalysts was designed and synthesized in this study, with comparable HCHO removal performance. Our results proved that foreign-element doping reduced Ti4+ to the lower oxidation state Ti(4- x)+, and that the internal charge kinetics was largely facilitated by the unbalanced electron distribution. Oxygen vacancies (OVs) were developed spontaneously to realize an electron-localized phenomenon in TiO2-x-OV, thereby boosting O2 adsorption and activation for the enhanced generation of reactive oxygen species (ROS). At the chemisorption stage, in-situ DRIFTS spectra and density functional theory calculation results revealed that surface adsorbed O2 (Oads) and lattice O (Olat) engaged in the isomerisation of HCHO to dioxymethylene (DOM) on TiO2-x-OV and TiO2, respectively. Time-resolved DRIFTS spectra under light irradiation revealed that the DOM was then converted to formate and thoroughly oxidized to CO2 and H2O in TiO2-x-OV. While bicarbonate byproducts were detected from DOM hydroxylation or possible side conversion of CO2 in TiO2, owing to insufficient consumption of surface hydroxyl. Our study enhances the understanding on the photocatalytic oxidation of HCHO, thereby promoting the practical application in indoor air purification.

Chemical characteristics and sources of nitrogen-containing organic compounds at a regional site in the North China Plain during the transition period of autumn and winter.

Organic nitrogen constitutes a significant fraction of the nitrogen budget in particulate matter (PM). However, the composition and sources of nitrogen-containing organic compounds (NOCs) in PM remain unclear currently in North China Plain (NCP), China. Rare local or regional studies on NOCs were conducted. In this study, ambient fine particles (PM2.5) were collected in Xianghe, a regional background site in NCP, from 26 October to 26 December 2017. The insights from this study include NOC molecule identification, concentration level, and NOC sources and origins. Specifically, we have identified and quantified >90 NOC species, with urea being the most abundant, accounting for 39.7 ± 4.7% of the total NOC followed by free amino acids (FAAs; 21.9 ± 1.5%), cyclic NOCs (15.3 ± 4.5%), amines (14.8 ± 1.5%), alkyl amides (5.8 ± 0.5%), isocyanates (1.7 ± 0.2%), and nitriles (1.1 ± 0.2%). The time series of FAAs was well correlated (r = 0.51-0.68, p < 0.01) with the organic marker of levoglucosan and was moderately correlated with Ox (r = 0.29-0.41, p < 0.01), suggesting biomass burning and secondary formation were important FAAs sources. We also show that amines can be oxidized and/or reacted by aqueous-phase processing to form secondary aerosols, which are further enhanced by the involvement of iron in the catalytic process. Using the receptor model of positive matrix factorization (PMF), six factors were identified including coal combustion, crustal sources, biomass burning, industry-related sources, traffic emissions, and secondary aerosols. Source apportionment of NOC shows biomass burning was the dominant factor, accounting for 31.8% of the total NOCs. This study provides a unique dataset of NOCs at this regional background site in the NCP, with the insights of NOC chemical composition and sources gained in this study being important for future NOC modeling as well as NOC health effects studies.

Photocatalytic Air Purification Using Functional Polymeric Carbon Nitrides.

The techniques for the production of the environment have received attention because of the increasing air pollution, which results in a negative impact on the living environment of mankind. Over the decades, burgeoning interest in polymeric carbon nitride (PCN) based photocatalysts for heterogeneous catalysis of air pollutants has been witnessed, which is improved by harvesting visible light, layered/defective structures, functional groups, suitable/adjustable band positions, and existing Lewis basic sites. PCN-based photocatalytic air purification can reduce the negative impacts of the emission of air pollutants and convert the undesirable and harmful materials into value-added or nontoxic, or low-toxic chemicals. However, based on previous reports, the systematic summary and analysis of PCN-based photocatalysts in the catalytic elimination of air pollutants have not been reported. The research progress of functional PCN-based composite materials as photocatalysts for the removal of air pollutants is reviewed here. The working mechanisms of each enhancement modification are elucidated and discussed on structures (nanostructure, molecular structue, and composite) regarding their effects on light-absorption/utilization, reactant adsorption, intermediate/product desorption, charge kinetics, and reactive oxygen species production. Perspectives related to further challenges and directions as well as design strategies of PCN-based photocatalysts in the heterogeneous catalysis of air pollutants are also provided.

Chemical and toxicological characterization of particulate emissions from diesel vehicles.

This paper presents a detailed chemical and toxicological characterization of the diesel particulate matter (PM) emitted from diesel vehicles running on a chassis dynamometer under different driving conditions. Chemical analyses were performed to characterize the contents of organic carbon (OC), elemental carbon (EC), and 31 polycyclic aromatic hydrocarbons (PAHs) in the collected PM samples. The OC-EC analysis results revealed that PM emissions from diesel vehicles in this study were dominated by OC and that the emission of vehicles equipped with diesel particulate filters had high OC/EC ratios. The PAH analysis results revealed that 4- and 5-ring PAHs were the dominant PAHs in the OC fraction of the PM samples. Particle toxicity was evaluated through three toxicological markers in human A549 cells, namely (1) acellular 2,7-dichlorofluorescein (DCFH) for oxidative potential, (2) interleukin-6 (IL-6) for inflammation, and (3) glutathione (GSH) for antioxidation after exposure. Statistical analyses revealed that vehicle sizes have statistically significant effects on the concentrations of the markers. Correlation analysis between PAHs and toxicological markers revealed that significant correlations existed between specific compounds and markers. Our results can be used as a reference by policy makers to formulate emission control strategies and as a dataset for other modeling studies.

The characteristics and sources of roadside VOCs in Hong Kong: Effect of the LPG catalytic converter replacement programme.

In order to improve local air quality of Hong Kong, more than 99% taxies and public light buses were changed from diesel to liquefied petroleum gas (LPG) fuel type in the early 2000s. In addition to the catalytic converters wear and tear, it is necessary to control air pollutants emitted from LPG vehicles. Therefore, an LPG catalytic converter replacement programme (CCRP) was fulfilled from October 2013 to April 2014 by the Hong Kong government. Roadside volatile compounds (VOCs) were measured by on-line measurement techniques before and after the programme to evaluate the effectiveness of the LPG CCRP. The mixing ratios of total measured VOCs were found decreased from 69.3 ± 12.6 ppbv to 43.9 ± 6.5 ppbv after the LPG CCRP with the decreasing percentage of 36.7%. In addition, the total mixing ratio of LPG tracers, namely propane, i-butane, and n-butane, accounted for 49% of total measured VOCs before the LPG CCRP and the weighting percentage decreased to 34% after the programme. Moreover, the source apportionment of roadside VOCs also reflects the large decreasing trend of LPG vehicular emissions after the air pollution control measure. Due to the application of PTR-MS on measuring real-time VOCs and oxygenated volatile compounds (OVOCs) in this study, the emission ratios of individual OVOCs were investigated and being utilized to differentiate primary and secondary/biogenic sources of roadside OVOCs in Hong Kong. The findings demonstrate the effectiveness of the intervention programme, and are helpful to further implementation of air pollution control strategies in Hong Kong.

In Situ Measurements of Molecular Markers Facilitate Understanding of Dynamic Sources of Atmospheric Organic Aerosols.

Reducing the amount of organic aerosol (OA) is crucial to mitigation of particulate pollution in China. We present time and air-origin dependent variations of OA markers and source contributions at a regionally urban background site in South China. The continental air contained primary OA markers indicative of source categories, such as levoglucosan, fatty acids, and oleic acid. Secondary OA (SOA) markers derived from isoprene and monoterpenes also exhibited higher concentrations in continental air, due to more emissions of their precursors from terrestrial ecosystems and facilitation of anthropogenic sulfate for monoterpenes SOA. The marine air and continental-marine mixed air had more abundant hydroxyl dicarboxylic acids (OHDCA), with anthropogenic unsaturated organics as potential precursors. However, OHDCA formation in continental air was likely attributable to both biogenic and anthropogenic precursors. The production efficiency of OHDCA was highest in marine air, related to the presence of sulfur dioxide and/or organic precursors in ship emissions. Regional biomass burning (BB) was identified as the largest contributor of OA in continental air, with contributions fluctuating from 8% to 74%. In contrast, anthropogenic SOA accounted for the highest fraction of OA in marine (37 ± 4%) and mixed air (31 ± 3%), overriding the contributions from BB. This study demonstrates the utility of molecular markers for discerning OA pollution sources in the offshore marine atmosphere, where continental and marine air pollutants interact and atmospheric oxidative capacity may be enhanced.

Effects of indoor activities and outdoor penetration on PM2.5 and associated organic/elemental carbon at residential homes in four Chinese cities during winter.

There is increasing public attention on exposure to PM2.5 and its related health impacts. It is essential to study the pollution levels, sources, and health implications of indoor PM2.5, especially for residential homes, as people tend to spend most of their time indoors. The indoor PM2.5 mass and organic/elemental carbon (OC/EC) during winter and early spring period of 2016-2017 at 68 residential households in four large Chinese cities (i.e. Hong Kong, Guangzhou, Shanghai, and Xi'an) were studied. Average indoor PM2.5 varied by two-fold, lowest in Hong Kong (34.0 ± 14.6 µg m-3) and highest in Xi'an (78.7 ± 49.3 µg m-3), with comparable levels for Guangzhou (47.2 ± 5.4 µg m-3) and Shanghai (50.3 ± 17.9 µg m-3). Lowest air exchange rate (AER, 0.8 ± 0.8 h-1) and PM2.5 indoor/outdoor (I/O) ratio (0.72 ± 0.23) were found for Xi'an households, indicating the limited influence from indoor sources, while importance of indoor PM2.5 sources is signified with the highest PM2.5 I/O ratio (1.32 ± 0.43) identified for Shanghai households. For households in four cities, OC and EC accounted for 29.5%-38.5% and 7.5%-8.9% of the indoor PM2.5 mass, indicating the significance of carbonaceous aerosols. Larger differences between indoor and outdoor OC (2.6-8.4%) than EC (-2.2-1.5%) indicate the presence of indoor OC sources. Decreasing trends of PM2.5 I/O ratio and indoor OC proportion were found as the worsening ambient air quality. On average, 11.8 µg m-3 (23.1%) and 3.02 µg m-3 (18.7%) higher indoor PM2.5 and OC concentrations were identified for households with other indoor combustions (e.g., tobacco smoking, incense burning) compared to those with only cooking activities. For Hong Kong and Shanghai households, increments of 13.2 µg m-3 (54.1%) of PM2.5 and 4.1 µg m-3 (45.4%) of OC were found at households with cooking activities as compared to households with no specific indoor combustion.

Real-World Vehicle Emissions Characterization for the Shing Mun Tunnel in Hong Kong and Fort McHenry Tunnel in the United States.

INTRODUCTION: Motor vehicle exhaust is an important source of air pollutants and greenhouse gases. Concerns over the health and climate effects of mobile-source emissions have prompted worldwide efforts to reduce vehicle emissions. Implementation of more stringent emission standards have driven advances in vehicle, engine, and exhaust after-treatment technologies as well as fuel formulations. On the other hand, vehicle numbers and travel distances have been increasing because of population and economic growth and changes in land use. These factors have resulted in changes to the amount and chemical composition of vehicle emissions.Roadway tunnel studies are a practical way to characterize real-world emissions from the on-road vehicle fleet in an environment isolated from other combustion pollution sources. Measurements in the same tunnel over time allow evaluation of vehicle emission changes and the effectiveness of emission reduction measures. Tunnel studies estimate the impacts of vehicle emissions on air quality and traffic-related exposures, generate source profile inputs for receptor-oriented source apportionment models, provide data to evaluate emission models, and serve as a baseline for future comparisons.The present study characterized motor vehicle emission factors and compositions in two roadway tunnels that were first studied over a decade ago. The specific aims were to (1) quantify current fleet air pollutant emission factors, (2) evaluate emission change over time, (3) establish source profiles for volatile organic compounds (VOCs) and particulate matter ≤2.5 µm in aerodynamic diameter (PM2.5), (4) estimate contributions of fleet components and non-tailpipe emissions to VOCs and PM2.5, and (5) evaluate the performance of the latest versions of mobile-source emission models (i.e., the EMission FACtors vehicle emission model used in Hong Kong [EMFAC-HK] and the MOtor Vehicle Emission Simulator used in the United States [MOVES]). METHODS: Measurements were conducted in the Shing Mun Tunnel (SMT) in Hong Kong and the Fort McHenry Tunnel (FMT) in Baltimore, Maryland, in the United States, representing the different fleet compositions, emission controls, fuels, and near-road exposure levels found in Hong Kong and the United States. These tunnels have extensive databases acquired in 2003-2004 for the SMT and 1992 for the FMT. The SMT sampling was conducted during the period from 1/19/2015 to 3/31/2015, and the FMT sampling occurred during the periods from 2/8/2015 to 2/15/2015 (winter) and 7/31/2015 to 8/7/2015 (summer). Concentrations of criteria pollutants (e.g., carbon monoxide [CO], nitrogen oxides [NOx], and particulate matter [PM]) were measured in real time, and integrated samples of VOCs, carbonyls, polycyclic aromatic hydrocarbons (PAHs), and PM2.5 were collected in canisters and sampling media for off-line analyses. Emission factors were calculated from the tunnel measurements and compared with previous studies to evaluate emission changes over time. Emission contributions by different vehicle types were assessed by source apportionment modeling or linear regression. Vehicle emissions were modeled by EMFAC-HK version 3.3 and MOVES version 2014a for the SMT and the FMT, respectively, and compared with measured values. The influences of vehicle fleet composition and environmental parameters (i.e., temperature and relative humidity) on emissions were evaluated. RESULTS: In the SMT, emissions of PM2.5, sulfur dioxide (SO2), and total non-methane hydrocarbons (NMHCs) markedly decreased from 2003-2004 to 2015: SO2 and PM2.5 were reduced by ~80%, and total NMHCs was reduced by ~44%. Emission factors of ethene and propene, key tracers for diesel vehicle (DV) emissions, decreased by ~65%. These reductions demonstrate the effectiveness of control measures, such as the implementation of low-sulfur fuel regulations and the phasing out of older DVs. However, the emission factors of isobutane and n-butane, markers for liquefied petroleum gas (LPG), increased by 32% and 17% between 2003-2004 and 2015, respectively, because the number of LPG vehicles increased. Nitrogen dioxide (NO2) to NOx volume ratios increased between 2003-2004 and 2015, indicating an increased NO2 fraction in primary exhaust emissions. Although geological mineral concentrations were similar between the 2003-2004 and 2015 studies, the contribution of geological materials to PM2.5 increased from 2% in 2003-2004 to 5% in 2015, signifying the continuing importance of non-tailpipe PM emissions as tailpipe emissions decrease. Emissions of CO, ammonia (NH3), nitric oxide (NO), NO2, and NOx, as well as carbonyls and PAHs in the SMT did not show statistically significant (at P < 0.05 based on Student's t-test) decreases from 2003-2004 to 2015. The reason for this is not clear and requires further investigation.A steady decrease in emissions of all measured pollutants during the past 23 years has been observed from tunnel studies in the United States, reflecting the effect of emission standards and new technologies that were introduced during this period. Emission reductions were more pronounced for the light-duty (LD) fleet than for the heavy-duty (HD) fleet. In comparison with the 1992 FMT study, the 2015 FMT study demonstrated marked reductions in LD emissions for all pollutants: emission factors for naphthalene were reduced the most, by 98%; benzene, toluene, ethylbenzene, and xylene (BTEX), by 94%; CO, NMHCs, and NOx, by 87%; and aldehydes by about 71%. Smaller reductions were observed for HD emission factors: naphthalene emissions were reduced by 95%, carbonyl emissions decreased by about 75%, BTEX by 60%, and NOx 58%.The 2015 fleet-average emission factors were higher in the SMT for CO, NOx, and summer PM2.5 than those in the FMT. The higher CO emissions in the SMT were possibly attributable to a larger fraction of motorcycles and LPG vehicles in the Hong Kong fleet. DVs in Hong Kong and the United States had similar emission factors for NOx. However, the non-diesel vehicles (NDVs), particularly LPG vehicles, had higher emission factors than those of gasoline cars, contributing to higher NOx emissions in the SMT. The higher PM2.5 emission factors in the SMT were probably attributable to there being more double-deck buses in Hong Kong.In both tunnels, PAHs were predominantly in the gas phase, with larger (four and more aromatic rings) PAHs mostly in the particulate phase. Formaldehyde, acetaldehyde, crotonaldehyde, and acetone were the most abundant carbonyl compounds in the SMT. In the FMT, the most abundant carbonyls were formaldehyde, acetone, acetaldehyde, and propionaldehyde. HD vehicles emitted about threefold more carbonyl compounds than LD vehicles did. In the SMT, the NMHC species were enriched with marker species for LPG (e.g., n-butane, isobutane, and propane) and gasoline fuel vapor (e.g., toluene, isopentane, and m/p-xylene), indicating evaporative losses. Source contributions to SMT PM2.5 mass were diesel exhaust (51.5 ± 1.8%), gasoline exhaust (10.0 ± 0.8%), LPG exhaust (5.0 ± 0.5%), secondary sulfate (19.9 ± 1.0%), secondary nitrate (6.3 ± 0.9%), and road dust (7.3 ± 1.3%). In the FMT, total NMHC emissions were 14% and 8% higher in winter than in summer for LD and HD vehicles, respectively. Elemental carbon (EC) and organic carbon (OC) were the major constituents of tunnel PM2.5. De-icing salt contributions to PM2.5 were observed in the FMT in winter.Emission estimates by the EMFAC-HK agreed with SMT measurements for CO2; the modeled emission factors for CO, NOx, and NMHCs were 1.5, 1.6, and 2.2 times the measurements, respectively; and the modeled emission factor for PM2.5 was 61% of the measured value in 2003. The EMFAC-HK estimates and SMT measurements for 2015 differed by less than 35%. The MOVES2014a model generally overestimated emissions of most of the pollutants measured in the FMT. No pollutants were significantly underestimated. The largest overestimation was observed for emissions measured during HD-rich driving conditions in winter. CONCLUSIONS: Significant reductions in SO2 and PM2.5 emissions between 2003 and 2015 were observed in the SMT, indicating the effectiveness of control measures on these two pollutants. The total NMHC emissions in the SMT were reduced by 44%, although isobutane and n-butane emissions increased because of the increase in the size of the LPG fleet. No significant reductions were observed for CO and NOx, results that differed from those for roadside ambient concentrations, emission inventory estimates, and EMFAC-HK estimates. In contrast, there was a steady decrease in emissions of most pollutants in the tunnels in the United States.

Active Complexes on Engineered Crystal Facets of MnOx-CeO2 and Scale-Up Demonstration on an Air Cleaner for Indoor Formaldehyde Removal.

Crystal facet-dominated surfaces determine the formation of surface-active complexes, and engineering specific facets is desirable for improving the catalytic activity of routine transition-metal oxides that often deactivate at low temperatures. Herein, MnOx-CeO2 was synthetically administered to tailor the exposure of three major facets, and their distinct surface-active complexes concerning the formation and quantitative effects of oxygen vacancies, catalytically active zones, and active-site behaviors were unraveled. Compared with two other low-index facets {110} and {001}, MnOx-CeO2 with exposed {111} facet showed higher activity for formaldehyde oxidation and CO2 selectivity. However, the {110} facet did not increase activity despite generating additional oxygen vacancies. Oxygen vacancies were highly stable on the {111} facet, and its bulk lattice oxygen at high migration rates could replenish the consumption of surface lattice oxygen, which was associated with activity and stability. High catalytically active regions were exposed at the {111}-dominated surfaces, wherein the predominated Lewis acid-base properties facilitated oxygen mobility and activation. The mineralization pathways of formaldehyde were examined by a combination of in situ X-ray photoemission spectroscopy and diffuse reflectance infrared Fourier transform spectrometry. The MnOx-CeO2-111 catalysts were subsequently scaled up to work as filter substrates in a household air cleaner. In in-field pilot tests, 8 h of exposure to an average concentration of formaldehyde after start-up of the air cleaner attained the Excellent Class of Indoor Air Quality Objectives in Hong Kong.

In Situ Intermediates Determination and Cytotoxicological Assessment in Catalytic Oxidation of Formaldehyde: Implications for Catalyst Design and Selectivity Enhancement under Ambient Conditions.

Formation and decay of formaldehyde oxides (CH2OO) affect the complete oxidation of formaldehyde. However, the speciation and reactivity of CH2OO are poorly understood because of its extremely fast kinetics and indirect measurements. Herein, three isomers of CH2OO (i.e., main formic acid, small dioxirane, and minor CH2OO Criegee) were in situ determined and confirmed as primary intermediates of the room-temperature catalytic oxidation of formaldehyde with two reference catalysts, that is, TiO2/MnO x-CeO2 and Pt/MnO x-CeO2. CH2OO Criegee is quite reactive, whereas formic acid and dioxirane have longer lifetimes. The production, stabilization, and removal of the three intermediates are preferentially performed at high humidity, matching well with the decay rate of CH2OO at approximately 6.6 × 103 s-1 in humid feed gas faster than 4.0 × 103 s-1 in dry feed. By contrast, given that a thinner water/TiO2 interface was well-defined in TiO2/MnO x-CeO2, fewer reductions in the active sites and catalytic activity were found when humidity was decreased. Furthermore, lethal intermediates mostly captured at the TiO2/MnO x-CeO2 surface suppressed the toxic off-gas emissions. This study provides practical insights into the rational design and selectivity enhancement of a reliable catalytic process for indoor air purification under unfavorable ambient conditions.

Roles of N-Vacancies over Porous g-C3N4 Microtubes during Photocatalytic NO x Removal.

The development of catalysts that effectively activate target pollutants and promote their complete conversion is an admirable objective in the environmental photocatalysis field. In this work, graphitic carbon nitride (g-C3N4) microtubes with tunable N-vacancy concentrations were controllably fabricated using an in situ soft-chemical method. The morphological evolution of g-C3N4, from the bulk to the porous tubular architecture, is discussed in detail with the aid of time-resolved hydrothermal experiments. We found that the NO removal ratio and apparent reaction rate constant of the g-C3N4 microtubes were 1.8 and 2.6 times higher than those of pristine g-C3N4, respectively. By combining detailed experimental characterization and density functional theory calculations, the effects of N-vacancies in the g-C3N4 microtubes on O2 and NO adsorption activation, electron capture, and electronic structure were systematically investigated. These results demonstrate that surface N-vacancies act as specific sites for the adsorption activation of reactants and photoinduced electron capture, while enhancing the light-absorbing capability of g-C3N4. Moreover, the porous wall structures of the as-prepared g-C3N4 microtubes facilitate the diffusion of reactants, and their tubular architectures favor the oriented transfer of charge carriers. The intermediates formed during photocatalytic NO removal processes were identified by in situ diffuse reflectance infrared Fourier transform spectroscopy, and different reaction pathways over pristine and N-deficient g-C3N4 are proposed. This study provides a feasible strategy for air pollution control over g-C3N4 by introducing N-vacancy and porous tubular architecture simultaneously.