The seasonal variability of black carbon (BC) aerosols in India is studied using high resolution (10 km) BC simulations conducted using the Weather Research and Forecasting Model coupled with Chemistry. The model reproduces the observed seasonality of surface BC fairly well over most parts of India but fails to capture the seasonality in the Himalayas and deviates from the observed BC magnitude at several sites. The errors in modeled BC are attributed to uncertainties in BC emissions and their diurnal cycle, planetary boundary layer height underestimation, and aerosol processes. Model results show distinct but opposite seasonality of BC in the lower (LT) and free troposphere (FT) with BC showing winter maximum and summer minimum in the LT and vice versa in the FT. Our analysis shows that BC seasonality is not driven by seasonality of the anthropogenic emissions but by changes in the regional meteorology through weakening of the horizontal transport and strengthening of the vertical transport of BC during summertime compared to winter. BC in both the LT and FT comes mostly from anthropogenic emissions followed by biomass burning emissions except during winter when long-distant sources become more important in the FT. BC in the FT is significantly affected by anthropogenic emissions from all parts of India. The source-receptor relationship changes seasonally, but the regional transport remains a significant contributor to BC loadings in the LT of India, highlighting the necessity of considering nonlocal sources along with local emissions when designing strategies for mitigating BC impacts on air quality.

[1] The influences of the springtime northern Indian biomass burning are shown for the first time over the central Himalayas by using three years (2007)(2008)(2009) . These biomass burning induced changes over the central Himalayan atmosphere during spring may also lead to enhanced short-wave absorption above clouds and might have an impact on the monsoonal rainfall.

We present an evaluation of the online regional model WRF-Chem over Europe with a focus on ground-level ozone (O-3) and nitrogen oxides (NOx). The model performance is evaluated for two chemical mechanisms, MOZART-4 and RADM2, for year-long simulations. Model-predicted surface meteorological variables (e.g., temperature, wind speed and direction) compared well overall with surface-based observations, consistent with other WRF studies. WRF-Chem simulations employing MOZART-4 as well as RADM2 chemistry were found to reproduce the observed spatial variability in surface ozone over Europe. However, the absolute O-3 concentrations predicted by the two chemical mechanisms were found to be quite different, with MOZART-4 predicting O-3 concentrations up to 20 mu g m(-3) greater than RADM2 in summer. Compared to observations, MOZART-4 chemistry overpredicted O-3 concentrations for most of Europe in the summer and fall, with a summertime domain-wide mean bias of +10 mu g m(-3) against observations from the AirBase network. In contrast, RADM2 chemistry generally led to an underestimation of O-3 over the European domain in all seasons. We found that the use of the MOZART-4 mechanism, evaluated here for the first time for a European domain, led to lower absolute biases than RADM2 when compared to ground-based observations. The two mechanisms show relatively similar behavior for NOx, with both MOZART-4 and RADM2 resulting in a slight underestimation of NOx compared to surface observations. Further investigation of the differences between the two mechanisms revealed that the net midday photochemical production rate of O-3 in summer is higher for MOZART-4 than for RADM2 for most of the domain. The largest differences in O-3 production can be seen over Germany, where net O-3 production in MOZART-4 is seen to be higher than in RADM2 by 1.8 ppbh 1 (3.6 mu g m(-3) h(-1)) or more. We also show that while the two mechanisms exhibit similar NOx sensitivity, RADM2 is approximately twice as sensitive to increases in anthropogenic VOC emissions as MOZART-4. Additionally, we found that differences in reaction rate coefficients for inorganic gas-phase chemistry in MOZART-4 vs. RADM2 accounted for a difference of 8 mu g m(-3), or 40% of the summertime difference in O-3 predicted by the two mechanisms. Differences in deposition and photolysis schemes explained smaller differences in O-3. Our results highlight the strong dependence of modeled surface O-3 over Europe on the choice of gas-phase chemical mechanism, which we discuss in the context of overall uncertainties in prediction of ground-level O-3 and its associated health impacts (via the health-related metrics MDA8 and SOMO35)

Abstract. Surface ozone is a secondary air pollutant produced during the atmospheric photochemical degradation of emitted volatile organic compounds (VOCs) in the presence of sunlight and nitrogen oxides (NOx). Temperature directly influences ozone production through speeding up the rates of chemical reactions and increasing the emissions of VOCs, such as isoprene, from vegetation. In this study, we used an idealised box model with different chemical mechanisms (Master Chemical Mechanism, MCMv3.2; Common Representative Intermediates, CRIv2; Model for OZone and Related Chemical Tracers, MOZART-4; Regional Acid Deposition Model, RADM2; Carbon Bond Mechanism, CB05) to examine the non-linear relationship between ozone, NOx and temperature, and we compared this to previous observational studies. Under high-NOx conditions, an increase in ozone from 20 to 40 °C of up to 20 ppbv was due to faster reaction rates, while increased isoprene emissions added up to a further 11 ppbv of ozone. The largest inter-mechanism differences were obtained at high temperatures and high-NOx emissions. CB05 and RADM2 simulated more NOx-sensitive chemistry than MCMv3.2, CRIv2 and MOZART-4, which could lead to different mitigation strategies being proposed depending on the chemical mechanism. The increased oxidation rate of emitted VOC with temperature controlled the rate of Ox production; the net influence of peroxy nitrates increased net Ox production per molecule of emitted VOC oxidised. The rate of increase in ozone mixing ratios with temperature from our box model simulations was about half the rate of increase in ozone with temperature observed over central Europe or simulated by a regional chemistry transport model. Modifying the box model set-up to approximate stagnant meteorological conditions increased the rate of increase of ozone with temperature as the accumulation of oxidants enhanced ozone production through the increased production of peroxy radicals from the secondary degradation of emitted VOCs. The box model simulations approximating stagnant conditions and the maximal ozone production chemical regime reproduced the 2 ppbv increase in ozone per degree Celsius from the observational and regional model data over central Europe. The simulated ozone–temperature relationship was more sensitive to mixing than the choice of chemical mechanism. Our analysis suggests that reductions in NOx emissions would be required to offset the additional ozone production due to an increase in temperature in the future.

The Indo‐Gangetic Plain (IGP) region is one of the most densely populated regions in the World, but ground‐based observations of air pollutants are highly limited in this region. Here, surface ozone observations made during March 2009–June 2011 at a semi‐urban site (Pantnagar; 29.0°N, 79.5°E, 231 m amsl) in the IGP region are presented. Ozone mixing ratios show a daytime photochemical buildup with ozone levels sometimes as high as 100 ppbv. Seasonal variation in 24‐h average ozone shows a distinct spring maximum (39.3 ± 18.9 ppbv in May) while daytime (1130–1630 h) average ozone shows an additional peak during autumn (48.7 ± 13.8 ppbv in November). The daytime, but not daily average, observed ozone seasonality is in agreement with the space‐borne observations of OMI tropospheric column NO2, TES CO (681 hPa), surface ozone observations at a nearby high altitude site (Nainital) in the central Himalayas and to an extent with results from a global chemistry transport model (MATCH‐MPIC). It is suggested that spring and autumn ozone maximum are mainly due to photochemistry, involving local pollutants and small‐scale dynamical processes. Biomass burning activity over the northern Indian region could act as an additional source of ozone precursors during spring. The seasonal ozone photochemical buildup is estimated to be 32–41 ppbv during spring and autumn and 9–14 ppbv during August–September. A correlation analysis between ozone levels at Pantnagar and Nainital along with the mixing depth data suggests that emissions and photochemical processes in the IGP region influence the air quality of pristine Himalayan region, particularly during midday hours of spring. The evening rate of change (8.5 ppbv hr−1) is higher than the morning rate of change, which is dissimilar to those at other urban or rural sites. Ozone seasonality over the IGP region is different than that over southern India. Results from the MATCH‐MPIC model capture observed ozone seasonality but overestimate ozone levels. Model simulated daytime ratios of H2O2/HNO3 are higher and suggesting that this region is in a NOx‐limited regime. A chemical box model (NACR Master Mechanism) is used to further corroborate this using a set of sensitivity simulations, and to estimate the integrated net ozone production in a day (72.9 ppbv) at this site.

Simultaneous in situ measurements of ozone, CO, and NO y have been made for the first time at a high altitude site Nainital (29. 37°N, 79.45°E, 1958 m above mean sea level) in the central Himalayas during [2009][2010][2011]. CO and NO y levels discern slight enhancements during the daytime, unlike in ozone. The diurnal patterns are attributed mainly to the dynamical processes including vertical winds and the boundary layer evolution. Springtime higher levels of ozone (57.5 ± 12.6 ppbv), CO (215.2 ± 147 ppbv), and NO y (1918 ± 1769.3 parts per trillion by volume (pptv)) have been attributed mainly to regional pollution supplemented with northern Indian biomass burning. However, lower levels of ozone (34.4 ± 18.9 ppbv), CO (146.6 ± 71 ppbv), and NO y (1128.6 ± 1035 pptv) during summer monsoon are shown to be associated with the arrival of air mass originated from marine regions. Downward transport from higher altitudes is estimated to enhance surface ozone levels over Nainital by 6.1-18.8 ppbv. The classification based on air mass residence time, altitude variations along trajectory, and boundary layer shows higher levels of ozone (57 ± 14 ppbv), CO (206 ± 125 ppbv), and NO y (1856 ± 1596 pptv) in the continental air masses when compared with their respective values (28 ± 13 ppbv, 142 ± 47 ppbv, and 226 ± 165 pptv) in the regional background air masses. In general, positive interspecies correlations are observed which suggest the transport of air mass from common source regions (except during winter). Ozone-CO and ozone-NO y slope values are found to be lower in comparison to those at other global sites, which clearly indicates incomplete in situ photochemistry and greater role of transport processes in this region. The higher CO/NO y value also confirms minimal influence of fresh emissions at the site. Enhancements in ozone, CO, and NO y during high fire activity period are estimated to be 4-18%, 15-76%, and 35-51%, respectively. Despite higher CO and NO y concentrations at Nainital, ozone levels are nearly similar to those at other global highaltitude sites.

Fine particulate matter (PM 2.5 , aerodynamic diameter ≤2.5 µm) impacts the climate, reduces visibility and severely influences human health. The Indo-Gangetic Plain (IGP), home to about one-seventh of the world's total population and a hotspot of aerosol loading, observes strong enhancements in the pM 2.5 concentrations towards winter. We performed high-resolution (12 km × 12 km) atmospheric chemical transport modeling (WRF-Chem) for the post-monsoon to winter transition to unravel the underlying dynamics and influences of regional emissions over the region. Model, capturing the observed variations to an extent, reveals that the spatial distribution of PM 2.5 having patches of enhanced concentrations (≥100 µgm −3) during post-monsoon, evolves dramatically into a widespread enhancement across the IGP region during winter. A sensitivity simulation, supported by satellite observations of fires, shows that biomass-burning emissions over the northwest IGP play a crucial role during post-monsoon. Whereas, in contrast, towards winter, a large-scale decline in the air temperature, significantly shallower atmospheric boundary layer, and weaker winds lead to stagnant conditions (ventilation coefficient lower by a factor of ~4) thereby confining the anthropogenic influences closer to the surface. Such changes in the controlling processes from post-monsoon to winter transition profoundly affect the composition of the fine aerosols over the IGP region. The study highlights the need to critically consider the distinct meteorological processes of west-to-east IGP and changes in dominant sources from post-monsoon to winter in the formulation of future pollution mitigation policies.

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