Vertical and horizontal distribution of sub-micron aerosol chemical composition and physical characteristics across Northern India, during the pre-monsoon and monsoon seasons

<p><strong>Abstract.</strong> The vertical distribution in the physical and chemical properties of submicron aerosol has been characterised across northern India for the first time using airborne in-situ measurements. This study focusses primarily on the Indo-Gangetic Plain, a low-lying area in the north of India which commonly experiences high aerosol mass concentrations prior to the monsoon season. Data presented are from the UK Facility for Airborne Atmospheric Measurements BAe-146 research aircraft that performed flights in the region during the 2016 pre-monsoon (11^th and 12^th June) and monsoon (30^th June to 11^th July) seasons.</p> <p> Inside the Indo-Gangetic Plain boundary layer, organic matter dominated the submicron aerosol mass (43&amp;thinsp;%) followed by sulphate (29&amp;thinsp;%), ammonium (14&amp;thinsp;%), nitrate (7&amp;thinsp;%) and black carbon (7&amp;thinsp;%). However, outside the Indo-Gangetic Plain, sulphate was the dominant species contributing 44&amp;thinsp;% to the total submicron aerosol mass in the boundary layer, followed by organic matter (30&amp;thinsp;%), ammonium (14&amp;thinsp;%), nitrate (6&amp;thinsp;%) and black carbon (6&amp;thinsp;%). Chlorine mass concentrations were negligible throughout the campaign. Black carbon mass concentrations were higher inside the Indo-Gangetic Plain (2&amp;thinsp;µg/m³ std) compared to outside (1&amp;thinsp;µg/m³ std). Nitrate appeared to be controlled by thermodynamic processes, with increased mass concentration in conditions of lower temperature and higher relative humidity. Increased mass and number concentrations were observed inside the Indo-Gangetic Plain and the aerosol was more absorbing in this region, whereas outside the Indo-Gangetic Plain the aerosol was larger in size and more scattering in nature, suggesting greater dust presence especially in northwest India. The aerosol composition remained largely similar as the monsoon season progressed, but the total aerosol mass concentrations decreased by ~&amp;thinsp;50&amp;thinsp;% as the rainfall arrived; the pre-monsoon average total mass concentration was 30&amp;thinsp;µg/m³ std compared to a monsoon average total mass concentration of 10&amp;ndash;20&amp;thinsp;µg/m³ std. However, this mass concentration decrease was less noteworthy (~&amp;thinsp;20&amp;ndash;30&amp;thinsp;%) over the Indo-Gangetic Plain, likely due to the strength of emission sources in this region. Decreases occurred in coarse mode aerosol, with the fine mode fraction increasing with monsoon arrival. In the aerosol vertical profile, inside the Indo-Gangetic Plain during the pre-monsoon, organic aerosol and absorbing aerosol species dominated in the lower atmosphere (<&amp;thinsp;1.5&amp;thinsp;km) with sulphate, dust and other scattering aerosol species enhanced in an elevated aerosol layer above 1.5&amp;thinsp;km with maximum aerosol height ~&amp;thinsp;6&amp;thinsp;km. As the monsoon progressed into this region, the elevated aerosol layer diminished, the aerosol maximum height reduced to ~&amp;thinsp;2&amp;thinsp;km and the total mass concentrations decreased by ~&amp;thinsp;50&amp;thinsp;%. The dust and sulphate-dominated aerosol layer aloft was removed upon monsoon arrival, highlighted by an increase in fine mode fraction throughout the profile.</p>

Oligomerization Reactions of Criegee Intermediates with Hydroxyalkyl Hydroperoxides: Mechanism, Kinetics, and Structure-Reactivity Relationship

<p><strong>Abstract.</strong> Although secondary organic aerosols (SOAs) are major components of PM_2.5 and organic aerosol (OA) particles and therefore profoundly influencing air quality, climate forcing and human health, the mechanism of SOAs formation via Criegee chemistry is poorly understood. Herein, we perform high-level theoretical calculations to study the reactivity and kinetics of four Criegee intermediates (CIs) reactions with four hydroxyalkyl hydroperoxides (HHPs) for the first time. The calculated results show that the sequential addition of CIs to HHPs affords oligomers containing CIs as chain units. The addition of -OOH group in HHPs to the central carbon atom of CIs is identified as the most energetically favorable channel, with a barrier height strongly dependent on both, CI substituent number (one or two) and position (<i>syn-</i> or <i>anti-</i>). In particular, the introduction of a methyl group into the <i>anti</i>-position significantly increase the rate coefficient, dramatic decrease is observed when the methyl group is introduced into the <i>syn</i>-position. Based on the collected data, the atmospheric lifetime of <i>anti</i>-CH₃CHOO in the presence of HHPs is estimated as ~<span class="thinspace"></span>5.9<span class="thinspace"></span>×<span class="thinspace"></span>103<span class="thinspace"></span>s. These findings are expected to broaden the reactivity profile and deepen our understanding of atmospheric SOAs formation processes.</p>

Tropospheric CO vertical profiles measured by IAGOS aircraft in 2002&ndash;2017 and the role of biomass burning

<p><strong>Abstract.</strong> This study investigates the role of biomass burning and long-range transport in the anomalies of carbon monoxide (CO) regularly observed along the tropospheric vertical profiles measured in the framework of IAGOS. Considering the high interannual variability of biomass burning emissions and the episodic nature of pollution long-range transport, one strength of this study is the amount of data taken into account, namely 30,000 vertical profiles at 9 clusters of airports in Europe, North America, Asia, India and southern Africa over the period 2002&amp;ndash;2017. </p> <p> As a preliminary, a brief overview of the spatio-temporal variability, latitudinal distribution, interannual variability and trends of biomass burning CO emissions from 14 regions is provided. The distribution of CO mixing ratios at different levels of the troposphere is also provided based on the entire IAGOS database (125 million CO observations). </p> <p> This study focuses on the free troposphere (altitudes above 2<span class="thinspace"></span>km) where the long-range transport of pollution is favoured. Anomalies at a given airport cluster are here defined as departures from the local seasonally-averaged climatological vertical profile. The intensity of these anomalies varies significantly depending on the airport, with maximum (minimum) CO anomalies of 110&amp;ndash;150 (48)<span class="thinspace"></span>ppbv in Asia (Europe). Looking at the seasonal variation of the frequency of occurrence, the 25<span class="thinspace"></span>% strongest CO anomalies appears reasonably well distributed along the year, in contrast to the 5<span class="thinspace"></span>% or 1<span class="thinspace"></span>% strongest anomalies that exhibit a strong seasonality with for instance more frequent anomalies during summertime in northern United-States, during winter/spring in Japan, during spring in South-east China, during the non-monsoon seasons in south-east Asia and south India, and during summer/fall at Windhoek, Namibia. Depending on the location, these strong anomalies are observed in different parts of the free troposphere. </p> <p> In order to investigate the role of biomass burning emissions in these anomalies, we used the SOFT-IO v1.0 IAGOS added-value products that consist of FLEXPART 20-days backward simulations along all IAGOS aircraft trajectories, coupled with anthropogenic (MACCity) and biomass burning (GFAS) CO emission inventories and vertical injections. SOFT-IO estimates the contribution (in ppbv) of the recent (less than 20 days) primary worldwide CO emissions, tagged per source region. Biomass burning emissions are found to play an important role in the strongest CO anomalies observed at most airport clusters. The regional tags indicate a large contribution from boreal regions at airport clusters in Europe and North America during summer season. In both Japan and south India, the anthropogenic emissions dominate all along the year, except for the strongest summertime anomalies observed in Japan that are due to Siberian fires. The strongest CO anomalies at airport clusters located in south-east Asia are induced by fires burning during spring in south-east Asia and during fall in equatorial Asia. In southern Africa, the Windhoek airport was mainly impacted by fires in southern hemisphere Africa and South America. </p> <p> To our knowledge, no other studies have used such a large dataset of in situ vertical profiles for deriving a climatology of the impact of biomass burning versus anthropogenic emissions on the strongest CO anomalies observed in the troposphere, in combination with information on the source regions. This study therefore provides both qualitative and quantitative information for interpreting the highly variable CO vertical distribution in several regions of interest.</p>

Considering the future of anthropogenic gas-phase organic compound emissions and the increasing influence of non-combustion sources on urban air quality

Decades of policy in developed regions has successfully reduced total anthropogenic emissions of gas-phase organic compounds, especially volatile organic compounds (VOCs), with an intentional, sustained focus on motor vehicles and other combustion-related sources. We examine potential secondary organic aerosol (SOA) and ozone formation in our case study megacity (Los Angeles), and demonstrate that non-combustion-related sources now contribute a major fraction of SOA and ozone precursors. Thus, they warrant greater attention beyond indoor environments to resolve large uncertainties in their emissions, oxidation chemistry, and outdoor air quality impacts in cities worldwide. We constrain the magnitude and chemical composition of emissions via several bottom-up approaches using: chemical analyses of products, emissions inventory assessments, theoretical calculations of emission timescales, and a survey of consumer product material safety datasheets. We demonstrate that the chemical composition of emissions from consumer products, and commercial/industrial products, processes, and materials is diverse across and within product/material-types with a wide range of SOA and ozone formation potentials that rivals other prominent sources, such as motor vehicles. With emission timescales from minutes to years, emission rates and source profiles need to be included, updated, and/or validated in emissions inventories, with expected regional/national variability. In particular, intermediate-volatility and semivolatile organic compounds (IVOCs and SVOCs) are key precursors to SOA but are excluded or poorly represented in emissions inventories, and exempt from emissions targets. We present an expanded framework for classifying VOC, IVOC, and SVOC emissions from this diverse array of sources that emphasizes a lifecycle approach over longer timescales and three emission pathways that extend beyond the short-term evaporation of VOCs: (1) solvent evaporation, (2) solute off-gassing, and (3) volatilization of degradation by-products. Furthermore, we find that ambient SOA formed from these non-combustion-related emissions could be misattributed to fossil fuel combustion due to the isotopic signature of their petroleum-based feedstocks.

Background aerosol over the Himalayas and Tibetan Plateau: observed characteristics of aerosol mass loading

To investigate the atmospheric aerosols of the Himalayas and Tibetan Plateau (HTP), an observation network was established within the region’s various ecosystems, including at the Ngari, Qomolangma (QOMS), Nam Co, and Southeastern Tibetan (SET) stations. In this paper we illustrate aerosol mass loadings by integrating <i>in situ</i> measurements with satellite and ground-based remote sensing datasets for the 2011&amp;ndash;2013 period, on both local and large scales. Mass concentrations of these surface atmospheric aerosols were relatively low and varied with land cover, showing a general tendency of Ngari and QOMS (barren sites) > Nam Co (grassland site) > SET (forest site). Daily averages of online PM_2.5 (particulates with aerodynamic diameters below 2.5&amp;thinsp;μm) at these sites were sequentially 18.2&amp;thinsp;±&amp;thinsp;8.9, 14.5&amp;thinsp;±&amp;thinsp;7.4, 11.9&amp;thinsp;±&amp;thinsp;4.9 and 11.7&amp;thinsp;±&amp;thinsp;4.7&amp;thinsp;μg&amp;thinsp;m^&amp;minus;3. Correspondingly, the ratios of PM_2.5 to total suspended particles (TSP) were 27.4&amp;thinsp;±&amp;thinsp;6.65&amp;thinsp;%, 22.3&amp;thinsp;±&amp;thinsp;10.9&amp;thinsp;%, 37.3&amp;thinsp;±&amp;thinsp;11.1&amp;thinsp;% and 54.4&amp;thinsp;±&amp;thinsp;6.72&amp;thinsp;%. Bimodal mass distributions of size-segregated particles were found at all sites, with a relatively small peak in accumulation mode and a more notable peak in coarse mode. Diurnal variations in fine aerosol masses generally displayed a bi-peak pattern at the QOMS, Nam Co and SET stations and a single-peak pattern at the Ngari station, controlled by the effects of local geomorphology, mountain-valley breeze circulation and aerosol emissions. Mineral content in PM_2.1 samples gave fractions of 26&amp;thinsp;% at the Ngari station and 29&amp;thinsp;% at the QOMS station, or ~&amp;thinsp;2&amp;ndash;3 times that of reported results at human-influenced sites. Furthermore, observed evidence confirmed the existence of the aerodynamic conditions necessary for the uplift of fine particles from a barren land surface. Combining surface aerosol data and atmospheric-column aerosol optical properties, the TSP mass and aerosol optical depth (AOD) of the Multi-angle Imaging Spectroradiometer (MISR) generally decreased as land cover changed from barren to forest, in inverse relation to the PM_2.5 ratios. The seasonality of aerosol mass parameters was land-cover dependent. Over forest and grassland areas, TSP mass, PM_2.5 mass, MISR-AOD and fine-mode AOD were higher in spring and summer, followed by relatively lower values in autumn and winter. At the barren site (the QOMS station), there were inconsistent seasonal variations between surface TSP mass (PM_2.5 mass) and atmospheric column AOD (fine-mode AOD). Our findings implicate that, HTP aerosol masses (especially their regional characteristics and fine particle emissions) need to be treated sensitively in relation to any assessments of their climatic effect and potential role as cloud condensation nuclei and ice nuclei.

Evidence of horizontal and vertical transport of water in the Southern Hemisphere Tropical Tropopause Layer (TTL) from high-resolution balloon observations

High-resolution in situ balloon measurements of water vapour, aerosol, methane and temperature in the upper Tropical Tropopause Layer (TTL) and lower stratosphere are used to evaluate the processes controlling the stratospheric water budget: horizontal transport (inmixing) and hydration by cross-tropopause overshooting updrafts. The obtained in situ evidences of these phenomena are analyzed using satellite observations by Aura MLS (Microwave Limb Sounder) and CALIPSO (Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observation) together with trajectory and transport modeling performed using CLaMS (Chemical Lagrangian Model of the Stratosphere) and HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) model. <br><br> Balloon soundings were conducted during March 2012 in Bauru, Brazil (22.3°&thinsp;S) in the frame of the TRO-Pico campaign for studying the impact of convective overshooting on the stratospheric water budget. The balloon payloads included two stratospheric hygrometers: FLASH-B (Fluorescence Lyman-Alpha Stratospheric Hygrometer for Balloon) and Pico-SDLA instrument as well as COBALD (Compact Optical Backscatter Aerosol Detector) sondes, complemented by Vaisala RS-92 radiosondes. Water vapour vertical profiles obtained independently by the two stratospheric hygrometers are in excellent agreement, ensuring credibility of the vertical structures observed. <br><br> A signature of in-mixing is inferred from a series of vertical profiles, showing coincident enhancements in water vapour and aerosol at the 425&thinsp;K (18.5&thinsp;km) level. Trajectory analysis unambiguously links these features to intrusions from the Southern Hemisphere extra-tropical stratosphere, containing more water and aerosol, as demonstrated by MLS and CALIPSO global observations. The in-mixing is successfully reproduced by CLaMS simulations, showing a relatively moist filament extending to 20&thinsp;S°. A signature of local cross-tropopause transport of water is observed in a particular sounding, performed on a convective day and revealing water vapour enhancements of up to 0.6&thinsp;ppmv as high as the 404&thinsp;K (17.8&thinsp;km) level. These are shown to originate from convective overshoots upwind detected by an S-band weather radar operating locally in Bauru. <br><br> The accurate in situ observations uncover two independent moisture pathways into the tropical lower stratosphere, whose manifestations are hardly detectable by space-borne sounders. We argue that the moistening by horizontal transport is limited by the weak meridional gradients of water, whereas the fast convective cross-tropopause transport, largely missed by global models, can have a substantial effect, at least at a regional scale.

Exploring atmospheric blocking with GPS radio occultation observations

Atmospheric blocking has been closely investigated in recent years due to its impact on weather and climate, such as heat waves, droughts, and flooding. We use, for the first time, satellite-based observations from Global Positioning System (GPS) radio occultation (RO) and explore their ability to resolve blocking in order to potentially open up new avenues complementing models and re-analyses. RO delivers globally available and vertically high resolved profiles of atmospheric variables such as temperature and geopotential height (GPH). Applying a standard blocking detection algorithm we find that RO data robustly capture blocking as demonstrated for two well-known blocking events over Russia in summer 2010 and over Greenland in late winter 2013. During blocking episodes, vertically resolved GPH gradients show a distinct anomalous behavior compared to climatological conditions up to 300 hPa and sometimes even further up to the tropopause. The accompanied increase in GPH of up to 300 m in the upper troposphere yields a pronounced tropopause height increase. Corresponding temperatures rise up to 10 K in the middle and lower troposphere. These results demonstrate the feasibility and potential of RO to detect and resolve blocking and in particular to explore the vertical structure of the atmosphere during blocking episodes. This new observation-based view is available globally at the same quality so that also blocking in the Southern Hemisphere can be studied with the same reliability as in the Northern Hemisphere.

The global tropospheric ammonia distribution as seen in the 13 year AIRS measurement record

Ammonia (NH3) plays an increasingly important role in the global biogeochemical cycle of reactive nitrogen as well as in aerosol formation and climate. We present extensive and nearly continuous global ammonia measurements made by the Atmospheric Infrared Sounder (AIRS) from the Aqua satellite to identify and quantify major persistent and episodic sources as well as to characterize seasonality. We examine the 13 year period from September 2002 through August 2015 with a retrieval algorithm using an optimal estimation technique with a set of three, spatially and temporally uniform a priori profiles. Vertical profiles show good agreement (~5–15 %) between AIRS NH3 and the in situ profiles from the winter 2013 DISCOVER-AQ field campaign in central California, despite the likely biases due to spatial resolution differences between the two instruments. AIRS captures the strongest consistent NH3 emissions from the anthropogenic (agricultural) source regions, such as, South Asia (India/Pakistan), China, the US, parts of Europe, SE Asia (Thailand/Myanmar/Laos), the central portion of South America, as well as Western and Northern Africa. These correspond primarily to croplands with extensive animal feeding operations and fertilizer applications where a summer maximum and secondary spring maximum are reliably observable. In the Southern Hemisphere (SH) regular agricultural fires contribute to a spring maximum. Regions of strong episodic emissions include Russia and Alaska as well as parts of South America, Africa, and Indonesia. Biomass burning, especially wildfires, dominate these episodic NH3 emissions.

Effectiveness of replacing catalytic converters in LPG-fueled vehicles in Hong Kong

Many taxis and public buses are powered by liquefied petroleum gas (LPG) in Hong Kong. With more vehicles using LPG, they have become the major contributor to ambient volatile organic compounds (VOCs) in Hong Kong. An intervention program aimed to reduce the emissions of VOCs and nitrogen oxides (NOx) from LPG-fueled vehicles was implemented by the Hong Kong Government in September 2013. Long-term real-time measurements indicated that the program was remarkably effective in reducing LPG-related VOCs, NOx and nitric oxide (NO) in the atmosphere. Receptor modeling results further revealed that propane, propene, i-butane, n-butane and NO in LPG-fueled vehicle exhaust emissions decreased by 37.3 ± 0.4, 50.2 ± 0.3, 32.9 ± 0.4, 41.1 ± 0.4 and 75.9 ± 0.3 %, respectively, during the implementation of the program. In contrast, despite the reduction of VOCs and NOx, the O3 production following the program increased by 0.25 ± 0.04 ppbv h−1 (4.8 %). Moreover, the production rate of HOx decreased due to the reduction of VOCs, whereas NO reduction resulted in a more significant decrease of the HOx in destruction compared to the decrease in production, and an increase of hydroxyl (OH) and hydroperoxyl (HO2). Analysis of O3-VOCs-NOx sensitivity in ambient air indicated VOC-limited regimes in the O3 formation before and during the program. Moreover, a maximum reduction percentage of NOx (i.e., 29.4 %) and the lowest reduction ratio of VOCs / NOx (i.e., ~ 3 : 1) in LPG-fueled vehicle emissions were determined to give a zero O3 increment. The findings are of great help to future formulation and implementation of control strategies on vehicle emissions in Hong Kong.

Contribution of oil and natural gas production to renewed increase of atmospheric methane (2007–2014): top-down estimate from ethane and methane column observations

Harmonized time series of column-averaged mole fractions of atmospheric methane and ethane over the period 1999–2014 are derived from solar Fourier transform infrared (FTIR) measurements at the Zugspitze summit (47° N, 2964 m a.s.l.) and at Lauder (45° S, 370 m a.s.l.). Long-term trend analysis reveals a consistent renewed methane increase since 2007 of 6.2 [5.6, 6.9] ppb yr−1 at the Zugspitze and 6.0 [5.3, 6.7] ppb yr−1 at Lauder (95 % confidence intervals). Several recent studies provide pieces of evidence that the renewed methane increase is most likely driven by two main factors: (i) increased methane emissions from tropical wetlands, followed by (ii) increased thermogenic methane emissions due to growing oil and natural gas production. Here, we quantify the magnitude of the second class of sources, using long-term measurements of atmospheric ethane as tracer for thermogenic methane emissions. In 2007, after years of weak decline, the Zugspitze ethane time series shows the sudden onset of a significant positive trend (2.3 [1.8, 2.8] × 10-2 ppb yr−1 for 2007–2014), while a negative trend persists at Lauder after 2007 (−0.4 [−0.6, −0.1] × 10-2 ppb yr−1). Zugspitze methane and ethane time series are significantly correlated for the period 2007–2014 and can be assigned to thermogenic methane emissions with an ethane-to-methane ratio of 10–21 %. We present optimized emission scenarios for 2007–2014 derived from an atmospheric two-box model. From our trend observations we infer a total ethane emission increase over the period 2007–2014 from oil and natural gas sources of 1–11 Tg yr−1 along with an overall methane emission increase of 24–45 Tg yr−1. Based on these results, the oil and natural gas emission contribution C to the renewed methane increase is deduced using three different emission scenarios with dedicated ranges of methane-to-ethane ratios (MER). Reference scenario 1 assumes an oil and gas emission combination with MER = 3.3–7.6, which results in a minimum contribution C > 28 % (given as lower bound of 99 % confidence interval). For the limiting cases of pure oil-related emissions with MER = 1.7–3.3 (scenario 2) and pure natural gas sources with MER = 7.6–12.1 (scenario 3) the results are C > 13 % and C > 53 %, respectively. Our results suggest that long-term observations of column-averaged ethane provide a valuable constraint on the source attribution of methane emission changes and provide basic knowledge for developing effective climate change mitigation strategies.