Primary Anthropogenic Emissions Research Articles

A fingerprint of source-specific health risk of PM2.5-bound components over a coastal industrial city

The influence of specific local land-use activities (continuously redistributing elements across environments) and environmental conditions (altering the chemical composition of airborne particulate matter) on the intrinsic health risk of PM2.5 exposure is sparsely reported. To fill this gap, we employed a novel integrated approach to address the influence of short-term changes in source-specific PM2.5 composition on the exposure-response risk, while controlling for weather conditions. We combine receptor-based source apportionment with conditional logistic regression in a space-time-stratified case-crossover design. This approach is different from previous studies as it: i) controls the impact of spatiotemporal variations in air pollution and human mobility using multilocation-specific fixed and disjointed space-time strata ii) addresses the spatial heterogeneity of personal exposure separating its variable effect from other predictors by allowing different baseline hazards for each space-time stratum; iii) aligns case/control periods with strong/regular episodes of source-specific PM-multipollutant fingerprint contributions rather than health outcomes. This enabled comprehensive examination of the association between source-specific PM2.5-bound species and cardiorespiratory disease hospitalizations. The epidemiological findings were that primary anthropogenic emissions [industrial (ORs 2.5 – 4.8)] were associated with higher 1-day moving average PM-induced risks. Natural-related sources [fresh / aged sea salt aerosol, dust, soil resuspension] and secondary sulfate formation were consistently associated with higher health risks (ORs 1.0 – 1.54) after 1 to 5-days since exposure. The results emphasize the importance of source-specific air quality management in complex areas and our research provides an adaptable universal tool to support targeted place-based policy interventions to mitigate air pollution impacts on health.

Immobilization of gaseous As2O3 on γ-Fe2O3 (001) surface by forming monodentate and bidentate complexes: Insight from DFT study

Coal combustion is one primary anthropogenic emission source of atmospheric arsenic. Ferromagnetic γ-Fe2O3 has been regarded as an effective and promising immobilization sorbent for As2O3(g) in flue gas with good magnetic properties. The reported mechanism explorations about gaseous arsenic capture in flue gas by density functional theory (DFT) are mainly based on forming one chemical bond between arsenic and sorbent. Recent studies demonstrated that multidentate arsenic complexes could be formed with iron oxides in solution. However, the possible formation pathway of multidentate complexes between gaseous As2O3 and γ-Fe2O3 was not been reported yet. This is the first study to investigate the thermodynamics and quantum mechanics of bidentate complexes between As2O3(g) and γ-Fe2O3 (001) by DFT. Three kinds of arsenic bidentate complexes were discovered at γ-Fe2O3 (001) surface, including “2 O to 2 Feoct”, “2 O to Fetet & Feoct,” and “As & O to 2 Feoct,” which were named as configuration A, B and C, respectively. Configuration B, “2 O to Fetet & Feoct”, showed the lowest adsorption energy (Eads) among the three kinds of bidentate complexes. The Mulliken population analysis further confirmed the electron transfer between the atoms of newly formed chemical bonds in bidentate configurations. In addition, the projected density of states (PDOS) analysis exhibiting resonance peaks also showed the formation of hybrid orbitals. The criteria for the determination of bidentate complexes were also proposed. The results evidence a convincing conclusion that monodentate and bidentate complexes with stable chemical bonds can be formed when As2O3(g) is immobilized by γ-Fe2O3 (001).

Machine Learning Classification of Air Quality Monitoring Stations to Achieve Ambient NO2 Objectives Using Emission Scenarios and Chemical Transport Model

Exceeding the latest Canadian Ambient Air Quality Standards (CAAQS) for NO2 concentration in Canadian cities motivates discussions on new policies and directives. Advanced air quality modeling and machine learning clustering algorithms integrating the Weather Research Forecast (WRF) and Community Multiscale Air Quality (CMAQ) models were used to classify air quality monitoring (AQM) stations based on pollution concentration modeling results. The sensitivity of ambient NO2 to the primary anthropogenic emission sources was investigated in Alberta, Canada. Emissions from two main sources, upstream oil and gas (UOG) and transportation sources, have been identified as the reason Alberta fails to meet the newly adopted NO2 CAAQS objectives. The air quality model was validated with ground-level observation data and the atmospheric model accurately replicates spatiotemporal NO2 variations. Despite contributing 62% of Alberta’s total NOx emissions, UOG influences ambient NO2 concentrations modestly in urban areas (<10%) but significantly affects rural regions. In contrast, transportation emission sources, responsible for 23% of NOx emissions, dominate ambient NO2 levels (up to 63%) in large cities. The discrepancy of emission contribution and ground-level concentrations, obtained from the chemical transport model, was resolved using a k-prototypes clustering algorithm to propose a new approach for categorizing AQM stations which led to improving the conventional classifications. The new approach considered the sensitivity of NO2 to emission reduction scenarios and provided an improved classification to be used for emission reduction interventions. Based on the updated classification, one set of AQM stations clearly showed sensitivity to NO2 emission reduction in the transportation sector despite their lower contributions to overall emissions. These stations were categorized as population exposure stations in large cities.

Deforestation as an Anthropogenic Driver of Mercury Pollution.

Deforestation reduces the capacity of the terrestrial biosphere to take up toxic pollutant mercury (Hg) and enhances the release of secondary Hg from soils. The consequences of deforestation for Hg cycling are not currently considered by anthropogenic emission inventories or specifically addressed under the global Minamata Convention on Mercury. Using global Hg modeling constrained by field observations, we estimate that net Hg fluxes to the atmosphere due to deforestation are 217 Mg year-1 (95% confidence interval (CI): 134-1650 Mg year-1) for 2015, approximately 10% of global primary anthropogenic emissions. If deforestation of the Amazon rainforest continues at business-as-usual rates, net Hg emissions from the region will increase by 153 Mg year-1 by 2050 (CI: 97-418 Mg year-1), enhancing the transport and subsequent deposition of Hg to aquatic ecosystems. Substantial Hg emissions reductions are found for two potential cases of land use policies: conservation of the Amazon rainforest (92 Mg year-1, 95% CI: 59-234 Mg year-1) and global reforestation (98 Mg year-1, 95% CI: 64-449 Mg year-1). We conclude that deforestation-related emissions should be incorporated as an anthropogenic source in Hg inventories and that land use policy could be leveraged to address global Hg pollution.

Effects of anthropogenic emissions and meteorological conditions on diurnal variation of formaldehyde (HCHO) in the Yangtze River Delta, China

Formaldehyde (HCHO) plays an important role in the troposphere, as it is a major precursor of ozone and heavily affects the health of lives on the earth. However, to the present, major factors that influence the diurnal variation of HCHO in the Yangtze River Delta (YRD) of China have not been investigated thoroughly. Moreover, sensitivities of the HCHO concentration in cities of YRD to the primary anthropogenic emissions of these cities are also unclear. Thus, we used a mesoscale meteorological model coupled with chemistry, WRF-Chem to capture the variation of HCHO in ten cities of YRD, so that the factors dominating the diurnal change of HCHO in these cities can be identified. We also performed sensitivity tests by varying the primary anthropogenic emission intensity of HCHO, to investigate the sensitivity of HCHO in each city to primary anthropogenic emissions of HCHO. The simulation results showed that the driving factors for the daytime peak of HCHO include photochemical reactions and VOCs＋OH reactions. The change in meteorological conditions causes a deviation of the temporal evolution of HCHO in many cities of YRD from the conventional trend (i.e., peak at noon and low in the rest). The major impact areas of HCHO anthropogenic emissions from the cities of YRD and the contributions to HCHO in these cities were also revealed.

Trends of source apportioned PM2.5 in Tianjin over 2013–2019: Impacts of Clean Air Actions

A long-term (2013–2019) PM2.5 speciation dataset measured in Tianjin, the largest industrial city in northern China, was analyzed with dispersion normalized positive matrix factorization (DN-PMF). The trends of source apportioned PM2.5 were used to assess the effectiveness of source-specific control policies and measures in support of the two China's Clean Air Actions implemented nationwide in 2013–2017 and 2018–2020, respectively. Eight sources were resolved from the DN-PMF analysis: coal combustion (CC), biomass burning (BB), vehicular emissions, dust, steelmaking and galvanizing emissions, a mixed sulfate-rich factor and secondary nitrate. After adjustment for meteorological fluctuations, a substantial improvement in PM2.5 air quality was observed in Tianjin with decreases in PM2.5 at an annual rate of 6.6%/y. PM2.5 from CC decreased by 4.1%/y. The reductions in SO2 concentration, PM2.5 contributed by CC, and sulfate demonstrated the improved control of CC-related emissions and fuel quality. Policies aimed at eliminating winter-heating pollution have had substantial success as shown by reduced heating-related SO2, CC, and sulfate from 2013 to 2019. The two industrial source types showed sharp drops after the 2013 mandated controls went into effect to phaseout outdated iron/steel production and enforce tighter emission standards for these industries. BB reduced significantly by 2016 and remained low due to the no open field burning policy. Vehicular emissions and road/soil dust declined over the Action's first phase followed by positive upward trends, showing that further emission controls are needed. Nitrate concentrations remained constant although NOX emissions dropped significantly. The lack of a decrease in nitrate may result from increased ammonia emissions from enhanced vehicular NOX controls. The port and shipping emissions were evident implying their impacts on coastal air quality. These results affirm the effectiveness of the Clean Air Actions in reducing primary anthropogenic emissions. However, further emission reductions are needed to meet global health-based air quality standards.

Stable Isotopes Reveal Photoreduction of Particle-Bound Mercury Driven by Water-Soluble Organic Carbon during Severe Haze.

Haze with high loading of particles may result in significant enrichment of particle-bound Hg (PBM), potentially impacting the atmospheric Hg transformation and transport. However, the dynamics of Hg transformation and the relative environmental effect during severe haze episodes remain unclear. Here, we report Hg isotopic compositions of atmospheric particles (PM2.5, PM10, and TSP) collected during a severe haze episode in Tianjin, China, to investigate the transformation and fate of Hg during haze events. All severe haze samples display significantly higher Δ199Hg (up to 1.50‰) than global urban PBM, which cannot be explained by primary anthropogenic emissions. The high Δ199Hg is likely caused by photoreduction of PBM promoted by water-soluble organic carbon (WSOC) during the particle accumulation period, as demonstrated by the positive correlations of Δ199Hg with WSOC and relative humidity and confirmed by our laboratory-controlled photoreduction experiment. The results show that, on average, 21% of PBM are likely photoreduced and re-emitted back to the atmosphere as Hg(0), potentially requiring revision of atmospheric Hg budgeting and modeling. This study highlights the release of large portions of PBM back to the gas phase through photoreduction, which needs to be taken into account while evaluating the atmospheric Hg cycle and the relative ecological effects.

Characteristics of VOC Composition at Urban and Suburban Sites of New Delhi, India in Winter

AbstractSimultaneous measurements of volatile organic compounds (VOCs) using two PTR‐TOF‐MS instruments were conducted at urban and suburban sites of New Delhi during the winter of 2018. The time series of VOC mixing ratios show substantial variations mainly influenced by local emissions and meteorological conditions. Mixing ratios of methanol (∼28 ppbv), acetaldehyde (7.7 ppbv), acetone (10.6 ppbv), isoprene (2.8 ppbv) and monoterpenes (0.84 ppbv) at the suburban site were higher than those at the urban site, while levels of aromatic VOCs were almost similar. The strong nighttime correlations of isoprene and monoterpenes with CO and benzene at the urban site indicate their predominant anthropogenic origin. Higher emission ratios of ∆VOCs/∆CO and ∆VOCs/∆benzene than those reported for vehicular exhaust suggest the contributions of other sources. In addition to vehicular emissions, episodes of biomass burning, industrial plumes and aged air strongly influenced the levels of VOCs at the suburban site. Despite the predominant primary anthropogenic emissions, the higher daytime enhancements of OVOCs/CO ratios indicate additional contributions of OVOCs from secondary/biogenic sources. The secondary formation of OVOCs in moderately aged air masses was noticeable at the suburban site. Using the source‐tracer‐ratio method, the estimated biogenic contributions of isoprene (71%) and acetone (65%) during daytime at the suburban site were significantly higher than those for the urban site. The photochemical box model simulations suggest that daytime ozone formation was under the VOC‐limited regime. The present study highlights the impact of different emission sources, photochemical processes and meteorological conditions on the composition and concentration of VOCs in the Delhi region.

Reduction in Anthropogenic Emissions Suppressed New Particle Formation and Growth: Insights From the COVID‐19 Lockdown

AbstractTo control the spread of the novel 2019 Coronavirus (COVID‐19), the Government of India enforced nationwide social and transportation restrictions (lockdown) in three phases from the evening of 24 March to 31 May 2020, which resulted in a significant reduction of primary emissions. Here, we performed the analyses of particle number size distribution measurements in the particle size range of 1.2–3 nm and 10–514 nm carried out from 15 April to 31 May 2020 (lockdown, LCD) and compared with measurements from the previous year during the same time period (15 April to 31 May 2019, business‐as‐usual, BAU) at University of Hyderabad in Hyderabad, India. The number concentrations of sub‐3 nm particles were comparable between LCD and BAU, but the number concentrations of particles greater than 10 nm diameter were lower by about 85% during LCD than BAU. It indicates that the reduction in primary anthropogenic emissions did not inhibit the formation of sub‐3 nm particles. But the frequency of occurrence of the new particle formation and growth (NPF&amp;G) events was three‐fold lower during LCD than BAU. The ratio of formaldehyde to nitrogen dioxide indicated that India falls in a NOx‐limited regime, which reduces ambient ozone concentrations (lower condensable vapors via ozone oxidation of volatile organic compounds). Besides, the lower temperature (lower hydroxyl radical concentration) and lower wind speed during LCD may have contributed to the suppression of NPF&amp;G events. Therefore, we emphasize the need to account for processes and interactions related to NPF&amp;G in formulating particulate pollution mitigation policies in urban environments.

Characteristics, correlations and health risks of PCDD/Fs and heavy metals in surface soil near municipal solid waste incineration plants in Southwest China

As primary anthropogenic emission source of toxic pollutants such as heavy metals and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), municipal solid waste (MSW) incineration has caused worldwide concern. However, a comprehensive analysis of the pollution characteristics and health risks of PCDD/Fs and heavy metals in soils around MSW incineration plants is lacking. In this study, 17 PCDD/Fs and 11 heavy metals in soil samples collected near MSW incineration plants in Sichuan province were investigated to evaluate their pollution characteristics and potential health risk. Sichuan was selected as the study area because the MSW incineration amount in this province ranks first among all inland provinces in China. The PCDD/Fs concentrations ranged from 0.30 to 7.50 ng I-TEQ/kg, which were significantly below risk screening and intervention thresholds. Regarding heavy metals, principal component analysis suggested that Hg, Pb and Zn were the primary metals emitted from the MSW incineration plants. Cluster analysis of PCDD/Fs and heavy metals showed that of PCDD/Fs homologs and heavy metals (e.g., Hg, Pb, Zn and Cd) were clustered into one group, indicating the coexistence and coaccumulation of heavy metals (especially Hg, Pb, Zn, and Cd) and PCDD/Fs in soil. These heavy metals are thus candidate tracers for PCDD/Fs in soil near MSW incineration plants. A health risk analysis found that the carcinogenic and non-carcinogenic risks of PCDD/Fs and heavy metals (except for Ni) in the soil samples were all within acceptable levels. This study provides new insights into correlations and health risks of PCDD/Fs and heavy metals in surface soil near MSW incineration plants. The findings have implications for future studies of environmental and human health risk analysis related to waste incineration.

Local emissions and secondary pollutants cause severe PM2.5 elevation in urban air at the south edge of the North China Plain: Results from winter haze of 2017–2018 at a mega city

Severe haze occurrence in the north of the North China Plain (NCP) is recognized as a consequence of the regional transport of pollutants initially from the south and then the rapid formation of secondary pollutants in the local air. However, the origin of pollutants causing haze in the southern NCP has not yet been elucidated even through careful data observation. Based on the contents of water-soluble inorganic ions in PM2.5 samples collected during two severe haze episodes in Zhengzhou, a mega city located on the southern edge of the NCP, we estimated the contributions of local primary emissions and secondary pollutants to haze occurrence. On average, Na+, K+, and Ca2+ mainly originated from anthropogenic sources, and their anthropogenic fractions had proportions of 97.5%, 93.9%, and 76.5% in their respective total mass. Anions Cl− and SO42− substantially originated from not only produced substantially via secondary formation but also from primary emissions, and their primary proportions in their respective total mass were 51.1% and 30.8%. In contrast, NH4+ and NO3− were dominated by secondary formation. The increase in PM2.5 was mainly caused by the formation of secondary inorganic (29.1%) and organic species (57.2%) and the primary anthropogenic emissions (12.5%). These results indicated that the haze at the southern edge of the NCP was mainly caused by pollutants in the local areas. Compared to the haze in the northern NCP, the haze in the southern NCP edge had a higher PM2.5 mass concentration and a higher proportion of secondary species, but a lower proportion of primary species, indicating the high heterogeneity of winter haze over the NCP.

Characterizing summer and winter carbonyl compounds in Beijing atmosphere

Carbonyl compounds (carbonyls) play important roles in atmospheric photochemistry, serving as reservoirs of radicals (OH, HO2, and RO2) and precursors of secondary organic aerosols (SOA). Field measurements of gaseous and particulate carbonyls were taken over urban Beijing during summer and winter, and field-measured gas-particle partitioning coefficients (Kp) were determined. Compared with theoretical values, field-measured Kp values were 4–6 orders of magnitude higher for the six detected carbonyls, which underlined the importance of heterogeneous reactions. In winter, the Kp values of carbonyl compounds were one order of magnitude higher than those in summer owing to the effect of temperature. This study applied the positive matrix factorization (PMF) model to the source apportionment of carbonyl compounds. Five factors were identified for both summer and winter, whereas the biogenic factor was only identified in summer and coal burning was only found in winter. In summer, secondary formation was the largest contributor (39%) to the measured total carbonyl compounds levels. In contrast, vehicular exhaust was the largest source of the measured total carbonyl compounds in winter (37%), although secondary formation still had an important contribution of 31%. The contribution of coal burning to ambient carbonyls was reduced by half compared with prior results. As the most abundant carbonyl compound in the atmosphere, formaldehyde in summer mainly came from secondary production (42%) and primary anthropogenic emissions (48%), while biogenic sources had a minor contribution (10%). However, 78% of formaldehyde was attributed to primary anthropogenic emissions in winter, which indicated that these winter emissions were more important sources of carbonyl compounds. Glyoxal was always dominated by secondary formation, with contributions of 56% in summer and 52% in winter.

Characterizing the level, photochemical reactivity, emission, and source contribution of the volatile organic compounds based on PTR-TOF-MS during winter haze period in Beijing, China

The atmospheric volatile organic compounds (VOCs) are the key participators in the formation of secondary organic aerosol and other atmospheric photochemical processes. However, it is still far from clear understanding of the VOCs in Northern China. In this study, VOCs were measured using a proton transfer reaction-time of flight-mass spectrometer (PTR-TOF-MS) in the downtown area of Beijing during a winter haze period in December 2016. The average mixing ratios of VOCs on the haze days were (ppb): methanol (51.75), formaldehyde (41.65), acetaldehyde (15.81), acetone (7.92), C8-aromatics (7.35), toluene (6.11), benzene (4.30), MEK (2.53), acetonitrile (2.05), C9-aromatics (1.54), benzaldehyde (1.12), isoprene (1.00), styrene (0.62). These concentrations represented the largest values among the cities around the world. VOC concentrations varied dramatically, with the largest value mainly appeared on days having the weakest diffusion condition. Due to the different solar radiation in this period, the photochemical reactivity of the VOCs showed the minimum and maximum values on haze and clear days, respectively. The primary anthropogenic emissions contributed more than half of the mixing ratios of most VOCs. However, formaldehyde received 56.6% contribution from the secondary or biogenic sources, and this contribution mainly increased at the noon hours when sunlight was stronger.

On the critical mass of greenhouse gas

In recent years, changes in the Earth’s climate have raised concern all around the globe. Climatologists have been drawing connections between global warming and a growing number of natural disasters, unexpected temperature fluctuations in some regions of the world and a number of other climatic aberrations. Within the scientific community, the opinions as to the nature and mechanism of the Earth’s climate change have split. Some contend that since the beginning of the industrial revolution, the carbon dioxide levels in the air have been steadily rising due to human production activities. Along with other gases, carbon dioxide has been inculpated for the greenhouse effect. In connection with this, a number of recent international conferences have adopted resolutions to reduce carbon dioxide emissions into the atmosphere. Another group of climatologists bases its findings on observations of solar activity, arguing that global warming is caused by a recurring spike in solar activity, with the current increase due to end soon, potentially giving way to a new ice age down the road. In the following work, we put forth yet another hypothesis regarding global warming. The influence of four main positive feedback loops caused by the secondary emission of water vapor, NI 2 , NI 4 , and decreased albedo on the earth climate system is shown on the basis of the general theory of feedback. If the present level of primary anthropogenic emissions of greenhouse gas (GhG) keeps, the total mass of atmospheric greenhouse gas can run up to such a critical value that the mentioned feedbacks, which give rise to self-amplification of the greenhouse effect, can cause the bifurcation transition of the climate system to the state of self-heating tending to the unlimited rise of mean temperature of the earth surface.

Spatial-temporal variation characteristics of air pollution in Henan of China: Localized emission inventory, WRF/Chem simulations and potential source contribution analysis

Henan is the most populous province and one of the most seriously polluted areas in China at present. In this study, we establish an integrated atmospheric emission inventory of primary air pollutants in Henan province for the target year of 2012. The inventory developed here accounts for detailed activity levels of 11 categories of primary anthropogenic emission sources, and determines the best available representation of emission factors. Further, we allocate the annual emissions into a high spatial resolution of 3km×3km with ArcGIS methodology and surrogate indices, such as regional population distribution and gross domestic product (GDP). Our results show that the emissions of VOCs, SO2, PM10, PM2.5, NOX, NH3, CO, BC and OC are about 1.15, 1.24, 1.29, 0.70, 1.93, 1.05, 7.92, 0.27 and 0.25milliontons, respectively. The majority of these pollutant emissions comes from the Central Plain Urban Agglomeration (CPUA) region, particularly Zhengzhou and Pingdingshan. By combining with the emission inventory with the WRF/Chem modeling and backward trajectory analysis, we investigate the temporal and spatial variability of air pollution in the province and explore the causes of higher pollutants concentrations in the region of CPUA during the heavily polluted period of January. The results demonstrate that intensive pollutants emissions and unfavorable meteorological conditions are the main causes of the heavy pollution. Besides, Weighted Potential Source Contribution Function (WPSCF) analysis indicates that local emissions remain the major contributor of PM2.5 in Henan province, although emissions from the neighboring provinces (e.g. Shanxi, Shaanxi, Anhui, and Shandong) are also important contributors.

Large biogenic contribution to boundary layer O3‐CO regression slope in summer

AbstractStrong correlation between O3 and CO was observed during the Deriving Information on Surface Conditions from Column and Vertically Resolved Observations Relevant to Air Quality (DISCOVER‐AQ) aircraft experiment in July 2011 over the Washington‐Baltimore area. The observed correlation does not vary significantly with time or altitude in the boundary layer. The observations are simulated well by a regional chemical transport model. We analyze the model results to understand the factors contributing to the observed O3‐CO regression slope, which has been used in past studies to estimate the anthropogenic O3 production amount. We trace separately four different CO sources: primary anthropogenic emissions, oxidation of anthropogenic volatile organic compounds, oxidation of biogenic isoprene, and transport from the lateral and upper model boundaries. Modeling analysis suggests that the contribution from biogenic isoprene oxidation to the observed O3‐CO regression slope is as large as that from primary anthropogenic CO emissions. As a result of decrease of anthropogenic primary CO emissions during the past decades, biogenic CO from oxidation of isoprene is increasingly important. Consequently, observed and simulated O3‐CO regression slopes can no longer be used directly with an anthropogenic CO emission inventory to quantify anthropogenic O3 production over the United States. The consistent enhancement of O3 relative to CO observed in the boundary layer, as indicated by the O3‐CO regression slope, provides a useful constraint on model photochemistry and emissions.

Trends and variability of atmospheric PM&amp;lt;sub&amp;gt;2.5&amp;lt;/sub&amp;gt; and PM&amp;lt;sub&amp;gt;10–2.5&amp;lt;/sub&amp;gt; concentration in the Po Valley, Italy

Abstract. The Po Valley is one of the largest European regions with a remarkably high concentration level of atmospheric pollutants, both for particulate and gaseous compounds. In the last decade stringent regulations on air quality standards and on anthropogenic emissions have been set by the European Commission, including also for PM2.5 and its main components since 2008. These regulations have led to an overall improvement in air quality across Europe, including the Po Valley and specifically PM10, as shown in a previous study by Bigi and Ghermandi (2014). In order to assess the trend and variability in PM2.5 in the Po Valley and its role in the decrease in PM10, we analysed daily gravimetric equivalent concentration of PM2.5 and of PM10–2.5 at 44 and 15 sites respectively across the Po Valley. The duration of the times series investigated in this work ranges from 7 to 10 years. For both PM sizes, the trend in deseasonalized monthly means, annual quantiles and in monthly frequency distribution was estimated: this showed a significant decreasing trend at several sites for both size fractions and mostly occurring in winter. All series were tested for a significant weekly periodicity (a proxy to estimate the impact of primary anthropogenic emissions), yielding positive results for summer PM2.5 and for summer and winter PM10–2.5. Hierarchical cluster analysis showed moderate variability in PM2.5 across the valley, with two to three main clusters, dividing the area in western, eastern and southern/Apennines foothill sectors. The trend in atmospheric concentration was compared with the time series of local emissions, vehicular fleet details and fuel sales, suggesting that the decrease in PM2.5 and in PM10 originates from a drop both in primary and in precursors of secondary inorganic aerosol emissions, largely ascribed to vehicular traffic. Potentially, the increase in biomass burning emissions in winter and the modest decrease in NH3 weaken an otherwise even larger drop in atmospheric concentrations.

GNAQPMS-Hg v1.0, a global nested atmospheric mercury transport model: model description, evaluation and application to trans-boundary transport of Chinese anthropogenic emissions

Abstract. Atmospheric mercury (Hg) is a toxic pollutant and can be transported over the whole globe due to its long lifetime in the atmosphere. For the purpose of assessing Hg hemispheric transport and better characterizing regional Hg pollution, a global nested atmospheric Hg transport model (GNAQPMS-Hg – Global Nested Air Quality Prediction Modeling System for Hg) has been developed. In GNAQPMS-Hg, the gas- and aqueous-phase Hg chemistry representing the transformation among three forms of Hg: elemental mercury (Hg(0)), divalent mercury (Hg(II)), and primary particulate mercury (Hg(P)) are calculated. A detailed description of the model, including mercury emissions, gas- and aqueous-phase chemistry, and dry and wet deposition is given in this study. Worldwide observations including extensive data in China have been collected for model evaluation. Comparison results show that the model reasonably simulates the global mercury budget and the spatiotemporal variation of surface mercury concentrations and deposition. Overall, model predictions of annual total gaseous mercury (TGM) and wet deposition agree with observations within a factor of 2, and within a factor of 5 for oxidized mercury and dry deposition. The model performs significantly better in North America and Europe than in East Asia. This can probably be attributed to the large uncertainties in emission inventories, coarse model resolution and to the inconsistency between the simulation and observation periods in East Asia. Compared to the global simulation, the nested simulation shows improved skill at capturing the high spatial variability of surface Hg concentrations and deposition over East Asia. In particular, the root mean square error (RMSE) of simulated Hg wet deposition over East Asia is reduced by 24 % in the nested simulation. Model sensitivity studies indicate that Chinese primary anthropogenic emissions account for 30 and 62 % of surface mercury concentrations and deposition over China, respectively. Along the rim of the western Pacific, the contributions from Chinese sources are 11 and 15.2 % over the Korean Peninsula, 10.4 and 8.2 % over Southeast Asia, and 5.7 and 5.9 % over Japan. But for North America, Europe and western Asia, the contributions from China are all below 5 %.

Eddy covariance flux measurements of gaseous elemental mercury using cavity ring-down spectroscopy.

A newly developed pulsed cavity ring-down spectroscopy (CRDS) system for measuring atmospheric gaseous elemental mercury (GEM) concentrations at high temporal resolution (25 Hz) was used to successfully conduct the first eddy covariance (EC) flux measurements of GEM. GEM is the main gaseous atmospheric form, and quantification of bidirectional exchange between the Earth's surface and the atmosphere is important because gas exchange is important on a global scale. For example, surface GEM emissions from natural sources, legacy emissions, and re-emission of previously deposited anthropogenic pollution may exceed direct primary anthropogenic emissions. Using the EC technique for flux measurements requires subsecond measurements, which so far has not been feasible because of the slow time response of available instrumentation. The CRDS system measured GEM fluxes, which were compared to fluxes measured with the modified Bowen ratio (MBR) and a dynamic flux chamber (DFC). Measurements took place near Reno, NV, in September and October 2012 encompassing natural, low-mercury (Hg) background soils and Hg-enriched soils. During nine days of measurements with deployment of Hg-enriched soil in boxes within 60 m upwind of the EC tower, the covariance of GEM concentration and vertical wind speed was measured, showing that EC fluxes over an Hg-enriched area were detectable. During three separate days of flux measurements over background soils (without Hg-enriched soils), no covariance was detected, indicating fluxes below the detection limit. When fluxes were measurable, they strongly correlated with wind direction; the highest fluxes occurred when winds originated from the Hg-enriched area. Comparisons among the three methods showed good agreement in direction (e.g., emission or deposition) and magnitude, especially when measured fluxes originated within the Hg-enriched soil area. EC fluxes averaged 849 ng m(-2) h(-1), compared to DFC fluxes of 1105 ng m(-2) h(-1) and MBR fluxes of 1309 ng m(-2) h(-1). This study demonstrated that a CRDS system can be used to measure GEM fluxes over Hg-enriched areas, with a conservative detection limit estimate of 32 ng m(-2) h(-1).

Impacts of future climate and emission changes on U.S. air quality

Changes in climate and emissions will affect future air quality. In this work, simulations of regional air quality during current (2001–2005) and future (2026–2030) winter and summer are conducted with the newly released CMAQ version 5.0 to examine the impacts of simulated future climate and anthropogenic emission projections on air quality over the U.S. Current meteorological and chemical predictions are evaluated against observations to assess the model's capability in reproducing the seasonal differences. WRF and CMAQ capture the overall observational spatial patterns and seasonal differences. Biases in model predictions are attributed to uncertainties in emissions, boundary conditions, and limitations in model physical and chemical treatments as well as the use of a coarse grid resolution. Increased temperatures (up to 3.18 °C) and decreased ventilation (up to 157 m in planetary boundary layer height) are found in both future winter and summer, with more prominent changes in winter. Increases in future temperatures result in increased isoprene and terpene emissions in winter and summer, driving the increase in maximum 8-h average O3 (up to 5.0 ppb) over the eastern U.S. in winter while decreases in NOx emissions drive the decrease in O3 over most of the U.S. in summer. Future PM2.5 concentrations in winter and summer and many of its components decrease due to decreases in primary anthropogenic emissions and the concentrations of secondary anthropogenic pollutants as well as increased precipitation in winter. Future winter and summer dry and wet deposition fluxes are spatially variable and increase with decreasing surface resistance and precipitation, respectively. They decrease with a decrease in ambient particulate concentrations. Anthropogenic emissions play a more important role in summer than in winter for future O3 and PM2.5 levels, with a dominance of the effects of significant emission reductions over those of climate change on future PM2.5 levels.