Aerosol-photolysis interaction reduces particulate matter during wintertime haze events.

Aerosol-radiation interaction (ARI) plays a significant role in the accumulation of fine particulate matter (PM2.5) by stabilizing the planetary boundary layer and thus deteriorating air quality during haze events. However, modification of photolysis by aerosol scattering or absorbing solar radiation (aerosol-photolysis interaction or API) alters the atmospheric oxidizing capacity, decreases the rate of secondary aerosol formation, and ultimately alleviates the ARI effect on PM2.5 pollution. Therefore, the synergetic effect of both ARI and API can either aggravate or even mitigate PM2.5 pollution. To test the effect, a fully coupled Weather Research and Forecasting (WRF)-Chem model has been used to simulate a heavy haze episode in North China Plain. Our results show that ARI contributes to a 7.8% increase in near-surface PM2.5 However, API suppresses secondary aerosol formation, and the combination of ARI and API results in only 4.8% net increase of PM2.5 Additionally, API increases the solar radiation reaching the surface and perturbs aerosol nucleation and activation to form cloud condensation nuclei, influencing aerosol-cloud interaction. The results suggest that API reduces PM2.5 pollution during haze events, but adds uncertainties in climate prediction.

Introductory lecture: air quality in megacities.

Urbanization is an ongoing global phenomenon as more and more people are moving from rural to urban areas for better employment opportunities and a higher standard of living, leading to the growth of megacities, broadly defined as urban agglomeration with more than 10 million inhabitants. Intense activities in megacities induce high levels of air pollutants in the atmosphere that harm human health, cause regional haze and acid deposition, damage crops, influence air quality in regions far from the megacity sources, and contribute to climate change. Since the Great London Smog and the first recognized episode of Los Angeles photochemical smog seventy years ago, substantial progress has been made in improving the scientific understanding of air pollution and in developing emissions reduction technologies. However, much remains to be understood about the complex processes of atmospheric oxidation mechanisms; the formation and evolution of secondary particles, especially those containing organic species; and the influence of emerging emissions sources and changing climate on air quality and health. While air quality has substantially improved in megacities in developed regions and some in the developing regions, many still suffer from severe air pollution. Strong regional and international collaboration in data collection and assessment will be beneficial in strengthening the capacity. This article provides an overview of the sources of emissions in megacities, atmospheric physicochemical processes, air quality trends and management in a few megacities, and the impacts on health and climate. The challenges and opportunities facing megacities due to lockdown during the COVID-19 pandemic is also discussed.

Formation of nanoparticles of blue haze enhanced by anthropogenic pollution.

The molecular processes leading to formation of nanoparticles of blue haze over forested areas are highly complex and not fully understood. We show that the interaction between biogenic organic acids and sulfuric acid enhances nucleation and initial growth of those nanoparticles. With one cis-pinonic acid and three to five sulfuric acid molecules in the critical nucleus, the hydrophobic organic acid part enhances the stability and growth on the hydrophilic sulfuric acid counterpart. Dimers or heterodimers of biogenic organic acids alone are unfavorable for new particle formation and growth because of their hydrophobicity. Condensation of low-volatility organic acids is hindered on nano-sized particles, whereas ammonia contributes negligibly to particle growth in the size range of 3-30 nm. The results suggest that initial growth from the critical nucleus to the detectable size of 2-3 nm most likely occurs by condensation of sulfuric acid and water, implying that anthropogenic sulfur emissions (mainly from power plants) strongly influence formation of terrestrial biogenic particles and exert larger direct and indirect climate forcing than previously recognized.

Heterogeneous HONO formation deteriorates the wintertime particulate pollution in the Guanzhong Basin, China.

Despite implementation of strict emission mitigation measures since 2013, heavy haze with high levels of secondary aerosols still frequently engulfs the Guanzhong Basin (GZB), China, during wintertime, remarkably impairing visibility and potentially causing severe health issues. Although the observed low ozone (O3) concentrations do not facilitate the photochemical formation of secondary aerosols, the measured high nitrous acid (HONO) level provides an alternate pathway in the GZB. The impact of heterogeneous HONO sources on the wintertime particulate pollution and atmospheric oxidizing capability (AOC) is evaluated in the GZB. Simulations by the Weather Research and Forecast model coupled with Chemistry (WRF-Chem) reveal that the observed high levels of nitrate and secondary organic aerosols (SOA) are reproduced when both homogeneous and heterogeneous HONO sources are considered. The heterogeneous sources (HET-sources) contribute about 98% of the near-surface HONO concentration in the GZB, increasing the hydroxyl radical (OH) and O3 concentration by 39.4% and 22.0%, respectively. The average contribution of the HET-sources to SOA, nitrate, ammonium, and sulfate in the GZB is 35.6%, 20.6%, 12.1%, and 6.0% during the particulate pollution episode, respectively, enhancing the mass concentration of fine particulate matters (PM2.5) by around 12.2%. Our results suggest that decreasing HONO level or the AOC becomes an effective pathway to alleviate the wintertime particulate pollution in the GZB.

Integrated urban services: Experience from four cities on different continents.

Rapid urbanization combined with climate change necessitates new types of urban services that make best use of science and technology. The Integrated Urban Hydro-Meteorological, Climate and Environmental Services and systems are a new initiative from the World Meteorological Organization (WMO) that seeks to provide science-based integrated urban services supporting safe, healthy and resilient cities. Various cities have already started development and implementation of such Integrated Urban Services and successfully test and use them following specific requirements of local stakeholders. This paper demonstrates the novel concept and approach of Integrated Urban Hydro-Meteorological, Climate and Environmental Services (IUS) from a set of four case study cities: Hong Kong, Toronto, Mexico City and Paris, that use different IUS configurations with good existing practice. These cities represent a range of countries, climates and geophysical settings. The aggregate main joint similarities of the IUS in these cities and synergy of the cities' experience, achievements and research findings are presented, as well as identification of existing gaps in knowledge and further research needs. A list of potential criteria for identifying and classifying IUS demonstration cities is proposed. It will aid future, more detailed analysis of the IUS experience, and selection of additional demonstration cities.

Integrated urban hydrometeorological, climate and environmental services: Concept, methodology and key messages.

Integrated Urban hydrometeorological, climate and environmental Services (IUS) is a World Meteorological Organization (WMO) initiative to aid development of science-based services to support safe, healthy, resilient and climate friendly cities. Guidance for Integrated Urban Hydrometeorological, Climate and Environmental Services (Volume I) has been developed with the intent to provide an overview of the concept, methods and good practices for producing and providing these services to respond to urban hazards across a range of time scales (weather to climate). This involves combining (dense) heterogeneous observation networks, high-resolution forecasts, multi-hazard early warning systems and climate services to assist cities in setting and implementing mitigation and adaptation strategies for the management and building of resilient and sustainable cities. IUS includes research, evaluation and delivery with a wide participation from city governments, national hydrometeorological services, international organizations, universities, research institutions and private sector stakeholders. An overview of the IUS concept with key messages, examples of good practice and recommendations are provided. The research community will play an important role to: identify critical research challenges; develop impact forecasts and warnings; promote and deliver IUS internationally, and; support national and local communities in the implementation of IUS thereby contributing to the United Nations' Sustainable Development Goals at all scales.

Real-world emissions of in-use off-road vehicles in Mexico.

Off-road vehicles used in construction and agricultural activities can contribute substantially to emissions of gaseous pollutants and can be a major source of submicrometer carbonaceous particles in many parts of the world. However, there have been relatively few efforts in quantifying the emission factors (EFs) and for estimating the potential emission reduction benefits using emission control technologies for these vehicles. This study characterized the black carbon (BC) component of particulate matter and NOx, CO, and CO2 EFs of selected diesel-powered off-road mobile sources in Mexico under real-world operating conditions using on-board portable emissions measurements systems (PEMS). The vehicles sampled included two backhoes, one tractor, a crane, an excavator, two front loaders, two bulldozers, an air compressor, and a power generator used in the construction and agricultural activities. For a selected number of these vehicles the emissions were further characterized with wall-flow diesel particle filters (DPFs) and partial-flow DPFs (p-DPFs) installed. Fuel-based EFs presented less variability than time-based emission rates, particularly for the BC. Average baseline EFs in working conditions for BC, NOx, and CO ranged from 0.04 to 5.7, from 12.6 to 81.8, and from 7.9 to 285.7 g/kg-fuel, respectively, and a high dependency by operation mode and by vehicle type was observed. Measurement-base frequency distributions of EFs by operation mode are proposed as an alternative method for characterizing the variability of off-road vehicles emissions under real-world conditions. Mass-based reductions for black carbon EFs were substantially large (above 99%) when DPFs were installed and the vehicles were idling, and the reductions were moderate (in the 20-60% range) for p-DPFs in working operating conditions. The observed high variability in measured EFs also indicates the need for detailed vehicle operation data for accurately estimating emissions from off-road vehicles in emissions inventories. IMPLICATIONS: Measurements of off-road vehicles used in construction and agricultural activities in Mexico using on-board portable emissions measurements systems (PEMS) showed that these vehicles can be major sources of black carbon and NOX. Emission factors varied significantly under real-world operating conditions, suggesting the need for detailed vehicle operation data for accurately estimating emissions inventories. Tests conducted in a selected number of sampled vehicles indicated that diesel particle filters (DPFs) are an effective technology for control of diesel particulate emissions and can provide potentially large emissions reduction in Mexico if widely implemented.

Modeling inorganic aerosols and their response to changes in precursor concentration in Mexico City.

Based on data from the 1997 Investigación sobre Materia Particulada y Deterioro Atmosférico-Aerosol and Visibility Evaluation Research (IMADA-EVER) campaign and the inorganic aerosol model ISORROPIA, the response of inorganic aerosols to changes in precursor concentrations was calculated. The aerosol behavior is dominated by the abundance of ammonia and thus, changes in ammonia concentration are expected to have a small effect on particle concentrations. Changes in sulfate and nitrate are expected to lead to proportional reductions in inorganic fine particulate matter (PM2.5). Comparing the predictions of ISORROPIA with the observations, the lowest bias and error are achieved when the aerosols are assumed to be in the efflorescence branch. Including crustal species reduces the bias and error for nitrate but does not improve overall model performance. The estimated response of inorganic PM2.5 to changes in precursor concentrations is affected by the inclusion of crustal species in some cases, although average responses are comparable with and without crustal species. Observed concentrations of particle chloride suggest that gas phase concentrations of hydrogen chloride may not be negligible, and future measurement campaigns should include observations to test this hypothesis. Our ability to model aerosol behavior in Mexico City and, thus, design control strategies, is constrained primarily by a lack of observations of gas phase precursors. Future campaigns should focus in particular on better understanding the temporal and spatial distribution of ammonia concentrations. In addition, gas phase observations of nitric acid are needed, and a measure of particle water content will allow stable versus metastable aerosol behavior to be distinguished.

Improving air quality in megacities: Mexico City case study.

The development and effective implementation of solutions to the air pollution problems in the Mexico City Metropolitan Area is essential to guarantee the health and welfare of its inhabitants. To achieve this, it is essential to have the active and informed participation of the civil society, the academic community, the private sector, and the government, because dealing with pollution requires the use of different strategies in multiple fields of action. The Mexico City case study brings together health, transportation, administration, and many other interdisciplinary approaches to understanding and defeating air pollution. Although focused on the Mexico City area, the work conducted under this case study has significance for developing nations generally. Although policies to reduce air pollution should be based on the best available scientific knowledge, political will and capacity must transform this knowledge into action. This case study has developed a series of recommendations emphasizing the interaction between different disciplines that have provided the foundation for the 10-year air quality management program prepared by the Mexican Metropolitan Environmental Commission.

Megacities and atmospheric pollution.

About half of the world's population now lives in urban areas because of the opportunity for a better quality of life. Many of these urban centers are expanding rapidly, leading to the growth of megacities, which are defined as metropolitan areas with populations exceeding 10 million inhabitants. These concentrations of people and activity are exerting increasing stress on the natural environment, with impacts at urban, regional and global levels. In recent decades, air pollution has become one of the most important problems of megacities. Initially, the main air pollutants of concern were sulfur compounds, which were generated mostly by burning coal. Today, photochemical smog--induced primarily from traffic, but also from industrial activities, power generation, and solvents--has become the main source of concern for air quality, while sulfur is still a major problem in many cities of the developing world. Air pollution has serious impacts on public health, causes urban and regional haze, and has the potential to contribute significantly to climate change. Yet, with appropriate planning, megacities can efficiently address their air quality problems through measures such as application of new emission control technologies and development of mass transit systems. This review is focused on nine urban centers, chosen as case studies to assess air quality from distinct perspectives: from cities in the industrialized nations to cities in the developing world. While each city--its problems, resources, and outlook--is unique, the need for a holistic approach to the complex environmental problems is the same. There is no single strategy in reducing air pollution in megacities; a mix of policy measures will be needed to improve air quality. Experience shows that strong political will coupled with public dialog is essential to effectively implement the regulations required to address air quality problems.

Estimating the health benefits from natural gas use in transport and heating in Santiago, Chile.

Chilean law requires the assessment of air pollution control strategies for their costs and benefits. Here we employ an online weather and chemical transport model, WRF-Chem, and a gridded population density map, LANDSCAN, to estimate changes in fine particle pollution exposure, health benefits, and economic valuation for two emission reduction strategies based on increasing the use of compressed natural gas (CNG) in Santiago, Chile. The first scenario, switching to a CNG public transportation system, would reduce urban PM2.5 emissions by 229 t/year. The second scenario would reduce wood burning emissions by 671 t/year, with unique hourly emission reductions distributed from daily heating demand. The CNG bus scenario reduces annual PM2.5 by 0.33 µg/m³ and up to 2 µg/m³ during winter months, while the residential heating scenario reduces annual PM2.5 by 2.07 µg/m³, with peaks exceeding 8 µg/m³ during strong air pollution episodes in winter months. These ambient pollution reductions lead to 36 avoided premature mortalities for the CNG bus scenario, and 229 for the CNG heating scenario. Both policies are shown to be cost-effective ways of reducing air pollution, as they target high-emitting area pollution sources and reduce concentrations over densely populated urban areas as well as less dense areas outside the city limits. Unlike the concentration rollback methods commonly used in public policy analyses, which assume homogeneous reductions across a whole city (including homogeneous population densities), and without accounting for the seasonality of certain emissions, this approach accounts for both seasonality and diurnal emission profiles for both the transportation and residential heating sectors.

The oxidative potential and biological effects induced by PM10 obtained in Mexico City and at a receptor site during the MILAGRO Campaign.

As part of a field campaign that studied the impact of Mexico City pollution plume at the local, sub-regional and regional levels, we studied transport-related changes in PM(10) composition, oxidative potential and in vitro toxicological patterns (hemolysis, DNA degradation). We collected PM(10) in Mexico City (T(0)) and at a suburban-receptor site (T(1)), pooled according to two observed ventilation patterns (T(0) → T(1) influence and non-influence). T(0) samples contained more Cu, Zn, and carbon whereas; T(1) samples contained more of Al, Si, P, S, and K (p < 0.05). Only SO(4)(-2) increased in T(1) during the influence periods. Oxidative potential correlated with Cu/Zn content (r = 0.74; p < 0.05) but not with biological effects. T(1) PM(10) induced greater hemolysis and T(0) PM(10) induced greater DNA degradation. Influence/non-influence did not affect oxidative potential nor biological effects. Results indicate that ventilation patterns had little effect on intrinsic PM(10) composition and toxicological potential, which suggests a significant involvement of local sources.

Assessment of diesel particulate matter exposure in the workplace: freight terminals.

A large study has been undertaken to assess the exposure to diesel exhaust within diesel trucking terminals. A critical component of this assessment is an analysis of the variation in carbonaceous particulate matter (PM) across trucking terminal locations; consistency in the primary sources can be effectively tracked by analyzing trends in elemental carbon (EC) and organic molecular marker concentrations. Ambient samples were collected at yard, dock and repair shop work stations in 7 terminals in the USA and 1 in Mexico. Concentrations of EC ranged from 0.2 to 12 microg m(-3) among the terminals, which corresponds to the range seen in the concentration of summed hopanes (0.5 to 20.5 ng m(-3)). However, when chemical mass balance (CMB) source apportionment results were presented as percent contribution to organic carbon (OC) concentrations, the contribution of mobile sources to OC are similar among the terminals in different cities. The average mobile source percent contribution to OC was 75.3 +/- 17.1% for truck repair shops, 65.4 +/- 20.4% for the docks and 38.4 +/- 9.5% for the terminal yard samples. A relatively consistent mobile source impact was present at all the terminals only when considering percentage of total OC concentrations, not in terms of absolute concentrations.

Characterization of aerosols containing Zn, Pb, and Cl from an industrial region of Mexico City.

Recent ice core measurements show lead concentrations increasing since 1970, suggesting new nonautomobile-related sources of Pb are becoming important worldwide (1). Developing a full understanding of the major sources of Pb and other metals is critical to controlling these emissions. During the March, 2006 MILAGRO campaign, single particle measurements in Mexico City revealed the frequent appearance of particles internally mixed with Zn, Pb, Cl, and P. Pb concentrations were as high as 1.14 microg/m3 in PM10 and 0.76 microg/m3 in PM2.5. Real time measurements were used to select time periods of interest to perform offline analysis to obtain detailed aerosol speciation. Many Zn-rich particles had needle-like structures and were found to be composed of ZnO and/or Zn(NO3)2 x 6H2O. The internally mixed Pb-Zn-Cl particles represented as much as 73% of the fine mode particles (by number) in the morning hours between 2-5 am. The Pb-Zn-Cl particles were primarily in the submicrometer size range and typically mixed with elemental carbon suggesting a combustion source. The unique single particle chemical associations measured in this study closely match signatures indicative of waste incineration. Our findings also show these industrial emissions play an important role in heterogeneous processing of NO(y) species. Primary emissions of metal and sodium chloride particles emitted by the same source underwent heterogeneous transformations into nitrate particles as soon as photochemical production of nitric acid began each day at approximately 7 am.

Interaction of hydrogen chloride with ice surfaces: the effects of grain size, surface roughness, and surface disorder.

Characterization of the interaction of hydrogen chloride (HCl) with polar stratospheric cloud (PSC) ice particles is essential to understanding the processes responsible for ozone depletion. The interaction of HCl with ice was studied using a coated-wall flow tube with chemical ionization mass spectrometry (CIMS) between 5x10(-8) and 10(-4) Torr HCl and between 186 and 223 K, including conditions recently shown to induce quasi-liquid layer (QLL) formation on single crystalline ice samples. Measurements were performed on smooth and rough (vapor-deposited) polycrystalline ice films. A numerical model of the coated-wall flow reactor was used to interpret these results and results of studies on zone-refined ice cylinders with grain sizes on the order of several millimeters (reported elsewhere). We found that HCl adsorption on polycrystalline ice films typically used in laboratory studies under conditions not known to induce surface disordering consists of two modes: one relatively strong mode leading to irreversible adsorption, and one relatively weak binding mode leading to reversible adsorption. We have indirect experimental evidence that these two modes of adsorption correspond to adsorption to sites at crystal faces and those at grain boundaries, but there is not enough information to enable us to conclusively assign each adsorption mode to a type of site. Unlike what was observed in the zone-refined ice study, there was no strong qualitative contrast found between the HCl uptake curves under QLL versus non-QLL conditions for adsorption on smooth and vapor-deposited ices. We also found indirect evidence that HCl hexahydrate formation on ice between 3x10(-7) and 2x10(-6) Torr HCl and between 186 and 190 K is a process involving hydrate nucleation and propagation on the crystal surface, rather than one originating in grain boundaries, as has been suggested for ice formed at lower temperatures. These results underscore the dependence of the HCl-ice interaction on the characteristics of the ice substrate.

Platinum group elements in airborne particles in Mexico City.

Automobile exhaust catalysts using platinum group elements (PGE) have been mandatory on new cars in the Mexico City Metropolitan Area (MCMA) since 1991. Platinum, Pd, Rh, Ir, and Os concentrations and the isotopic composition of Os were determined in PM10 samples from the MCMA. Samples were prepared by isotope dilution NiS fire assay, and analysis was performed by magnetic sector ICP-MS using a single collector instrument for Pt, Pd, Rh, and Ir analysis and a multicollector instrument for Os analysis. Pt, Pd, and Rh concentrations at a downtown location (Merced) increased from < or =1.7 pg of Pt m(-3), 2.7 (4.0) pg of Pd m(-3), and 1.2+/-0.9 pg of Rh m(-3) in 1991 to 9.6 +/- 1.8 pg of Pt m(-3), 10.2+/-1.8 pg of Pd m(-3), and 2.8 +/-0.6 pg of Rh m(-3) in 2003. Concentrations at five sites in MCMA in 2003 averaged 9.3+/-1.9 pg of Pt m(-3), 11+/-4 pg of Pd m(-3), and 3.2+/- 1.0 pg of Rh m(-3). In contrast, Ir and Os concentrations and Os isotopic composition remained relatively constant and were 0.08+/-0.04 pg of Ir m(-3), 0.030 +/-0.007 pg of Os m(-3), and 0.60+/-0.04, respectively, in the MCMA in 2003. Elevated Pt, Pd, and Rh concentrations in the MCMA are attributed to automobile catalysts. A Pt-Pd-Rh concentration peak in 1993 suggests that early catalysts emitted a larger amount of PGE, possibly due to factors inherent in the technology or the use of inappropriate gasoline. Therefore, this study suggests that the current introduction of automobile catalysts in developing countries may result in elevated PGE concentrations if it is not accompanied by infrastructures and policy measures supporting their efficient use.

Oxidation mechanism of aromatic peroxy and bicyclic radicals from OH-toluene reactions.

Theoretical calculations have been performed to investigate mechanistic features of OH-initiated oxidation reactions of toluene. Aromatic peroxy radicals arising from initial OH and subsequent O(2) additions to the toluene ring are shown to cyclize to form bicyclic radicals rather than undergoing reaction with NO under atmospheric conditions. Isomerization of bicyclic radicals to more stable epoxide radicals possesses significantly higher barriers and, hence, has slower rates than O(2) addition to form bicyclic peroxy radicals. At each OH attachment site, only one isomeric pathway via the bicyclic peroxy radical is accessible to lead to ring cleavage. The study provides thermochemical and kinetic data for quantitative assessment of the photochemical production potential of ozone and formation of toxic products and secondary organic aerosol from toluene oxidation.

Vehicle traffic as a source of particulate polycyclic aromatic hydrocarbon exposure in the Mexico City metropolitan area.

Surface properties of aerosols in the Mexico City metropolitan area have been measured in a variety of exposure scenarios related to vehicle emissions in 2002, using continuous, real-time instruments. The objective of these experiments is to describe ambient and occupational particulate polycyclic aromatic hydrocarbon (PAH) concentrations associated with vehicular traffic and facilities using diesel vehicles. Median total particulate PAH concentrations along Mexico City's roadways range from 60 to 910 ng m(-3), averaged over a minimum of 1 h. These levels are approximately 5 times higher than concentrations measured in the United States and among the highest measured ambient values reported in the literature. The ratio of particulate PAH concentration to aerosol active surface area is much higher along roadways and in other areas of fresh vehicle emissions, compared to ratios measured at sites influenced more by aged emissions or noncombustion sources. For particles freshly emitted by vehicles, PAH and elemental carbon (EC) concentrations are correlated because they both originate during the combustion process. Comparison of PAH versus EC and active surface area concentrations at different locations suggests that surface PAH concentrations may diminish with particle aging. These results indicate that exposure to vehicle-related PAH emissions on Mexico City's roadways may present an important public health risk.