Measurements of Volatile Organic Compounds at a rural site in India: Variability and sources during the seasonal transition.

Volatile Organic Compounds (VOCs) play a vital role in tropospheric ozone formation that controls the oxidative capacity of the troposphere. A total of 31 potential ozone precursor VOCs have been measured at a tropical rural site, Gadanki (13.5°N, 79.2°E) in Southern peninsular India. This study provides the primary information about different VOCs, their chemical classification and potential sources. There is a strong seasonal and diurnal variability among the VOC composition. n-Decane and n-dodecane dominate the other VOCs and contribute to a large fraction (>50 %) of the concentration of total VOCs (TVOCs) in winter and summer, monsoon is dominated by n-dodecane and post monsoon season has been dominated by ethane emissions. The source apportionment using interspecies correlation and Positive Matrix Factorisation (PMF) analysis resulted in four potential emission source factors namely biogenic, biomass burning/biofuel, fossil fuel and natural gas emissions. Winter and summer seasons have been dominated by VOCs originating from biomass burning/biofuel factors, monsoon has been dominated by biogenic emissions and post-monsoon season has been dominated by natural gas emissions. Even though it is a rural site, there are significant finger prints of anthropogenic emissions in the form of fossil fuel and natural gas most probably due to an adjacent national highway and long range transport. However, for the overall period, the VOCs emitted from biogenic and biomass burning together dominate the other two factors, indicating the expected source factor behaviour of a rural atmosphere.

Spatial variability of trace gases (NO2, O3 and CO) over Indian region during 2020 and 2021 COVID-19 lockdowns.

COVID-19 lockdown has given us an opportunity to investigate the pollutant concentrations in response to the restricted anthropogenic activities. The atmospheric concentration levels of nitrogen dioxide (NO2), carbon monoxide (CO) and ozone (O3) have been analysed for the periods during the first wave of COVID-19 lockdown in 2020 (25th March-31st May 2020) and during the partial lockdowns due to second wave in 2021 (25th March-15th June 2021) across India. The trace gas measurements from Ozone Monitoring Instrument (OMI) and Atmosphere InfraRed Sounder (AIRS) satellites have been used. An overall decrease in the concentration of O3 (5-10%) and NO2 (20-40%) have been observed during the 2020 lockdown when compared with business as usual (BAU) period in 2019, 2018 and 2017. However, the CO concentration increased up to 10-25% especially in the central-west region. O3 and NO2 slightly increased or had no change in 2021 lockdown when compared with the BAU period, but CO showed a mixed variation prominently influenced by the biomass burning/forest fire activities. The changes in trace gas levels during 2020 lockdown have been predominantly due to the reduction in the anthropogenic activities, whereas in 2021, the changes have been mostly due to natural factors like meteorology and long-range transport, as the emission levels have been similar to that of BAU. Later phases of 2021 lockdown saw the dominant effect of rainfall events resulting in washout of pollutants. This study reveals that partial or local lockdowns have very less impact on reducing pollution levels on a regional scale as natural factors like atmospheric long-range transport and meteorology play deciding roles on their concentration levels.

Influence of background dynamics on the vertical distribution of trace gases (CO/WV/O3) in the UTLS region during COVID-19 lockdown over India.

The COVID-19 pandemic lockdown has led to the significant reductions in the pollutant levels across the globe. Several studies have been carried out for examining and quantifying the improvement in the air quality due to the reduction of the pollution at the surface. Unlike most of the studies carried out earlier on COVID-19 lockdown, this study investigates the role of the dynamics on the vertical distribution of the trace gases (Carbonmonoxide (CO), Water Vapor (WV) and Ozone (O3)) over India in the Boundary Layer (BL), Middle Troposphere (MT) and Upper Troposphere (UT) during COVID-19 lockdown using satellite observations and re-analysis data products obtained during 2010-2020. Substantial differences in the time series and variability have been observed over different zones of India in different atmospheric layers. The changes observed in these species are large over Central India compared to South India and Indo-Gangetic plain regions. An enhancement in CO (~25-40%) and WV (50-60%) has been noticed over Central India in the UT at 147 hPa and 215 hPa, respectively, during lockdown. The strong updrafts before the lockdown and the extended weak zonal wind aloft over this region are found responsible for the observed enhancement in these trace gases in the UT. In spite of the non-availability of the anthropogenic pollution during the lockdown, this study highlights the transport of pollutants through long-range transport (always present even before lockdown) dominance over the Indian region not only near the surface but also aloft due to associated atmospheric dynamics.

Regional estimation of methane emissions over the peninsular India using atmospheric inverse modelling.

Accurate renditions of country-scale methane (CH4) emissions are critical in understanding the regional CH4 budget and essential for adapting national climate mitigation policies to curtail the atmospheric build-up of this greenhouse gas with high warming potential. India housing 30% of the Asian population is currently appraised as a region of CH4 source based on the inventories. To date, there have not been many reported efforts to estimate the regional CH4 emissions using direct measurements of boundary layer CH4 concentrations at multiple locations over India. Here, 2 years (2017-2018) of in situ CH4 observations from three distantly placed stations over the peninsular India is combined with state-of-the-art inversion using a Lagrangian particle dispersion model for the estimation of CH4 emission. This study updates CH4 emission over the peninsular India (land area south of 21.5°N) as ~ 10.63 Terra gram (Tg) CH4 year-1, which is 0.13 Tg CH4 year-1 higher than the existing inventory-based emission. On seasonal scale, the changes from the existing CH4 emission inventories are 0.12, 0.05, 0.055 and 0.28 Tg CH4 year-1 during winter, pre-monsoon, monsoon and post-monsoon seasons respectively. Spatial distributions of seasonal variability of posterior emissions suggest an enhancement over the eastern region of peninsular India compared to the western part. The study with observations from three stations over the peninsular India provides an update on the inventory-based estimation of CH4 emissions and urges the importance of more observations over the Indian region for the accurate estimation of fluxes.

Phase-wise analysis of the COVID-19 lockdown impact on aerosol, radiation and trace gases and associated chemistry in a tropical rural environment.

Phase-wise variations in different aerosol (BC, AOD, PM1, PM2.5 and PM10), radiation (direct and diffused) and trace gases (NO, NO2, CO, O3, SO2, CO2 and CH4) and their associated chemistry during the COVID-19 lockdown have been investigated over a tropical rural site Gadanki (13.5° N, 79.2° E), India. Unlike most of the other reported studies on COVID-19 lockdown, this study provides variations over a unique tropical rural environment located at a scientifically strategic location in the Southern Indian peninsula. Striking differences in the time series and diurnal variability have been observed in different phases of the lockdown. The levels of most species that are primarily emitted from anthropogenic activities reduced significantly during the lockdown which also impacted the levels and diurnal variability of secondary species like O3. When compared with the same periods in 2019, short-lived trace gas species such as NO, NO2, SO2 which have direct anthropogenic emission influence have shown the reduction over 50%, whereas species like CO and O3 which have direct as well as indirect impacts of anthropogenic emissions have shown reductions up to 10%. Long-lived species (CO2 and CH4) have shown negligible difference (<1%). BC and AOD have shown reductions over 20%. Particulate Matter (1, 2.5 and 10) reductions have been in the range of 40 to 50% when compared to the pre-lockdown period. The changes in shortwave downward radiation at the surface, diffuse component due to the scattering and diffuse fraction have been +2.2%, -4.1% and -2.4%, respectively, in comparison with 2019. In contrast with the studies over urban environments, air quality category over the rural environment remained same during the lockdown despite reduction in pollutants level. All the variations observed for different species and their associated chemistry provides an excellent demonstration of rural atmospheric chemistry and its intrinsic links with the precursor concentrations and dynamics.

Source apportionment of rainwater chemical composition to investigate the transport of lower atmospheric pollutants to the UTLS region.

Efforts to understand the chemical composition of Asian Tropopause Aerosol Layer (ATAL) in the Upper Troposphere Lower Stratosphere (UTLS) region have revealed the dominance of nitrates in the samples collected from ATAL layer during the recent balloon campaigns. Potential sources have been thought to be in-situ formation, convective uplift and long-range transport. Rainwater chemical composition consists water-soluble chemical ions that are wet scavenged during rain events and gives an indirect indication of lower atmospheric pollutants. Keeping this in focus, total monsoon precipitation chemistry at Gadanki (13.5°N, 79.2°E) has been studied to understand the convective uplift possibilities to the UTLS region. About 32 rainwater samples collected during July to December 2017 were analysed for their chemical composition using Ion Chromatography. Total 16 ions comprising of 5 anions (F-, Cl-, NO3-, SO42- and PO43-), 6 cations (Na+, K+, Ca2+, Mg2+, Li+ and NH4+) and 5 trace metals (Cd2+, Ni2+, Co2+, Mn2+ and Zn2+) have been detected in different rainwater samples. Rainwater chemical composition data has been subjected to the Principal Component Analysis (PCA) to understand the correlations between different chemical species and to identify the possible sources of origin qualitatively. It has been observed that the chemical composition of the rainwater is very different from the chemical composition of the ATAL layer indicating non-existence of convective transport of lower level pollutants to the UTLS region at Gadanki. This observation is also well supported by the vertical distribution of CALIPSO derived aerosol types and ERA interim vertical pressure velocities during the sampling period.

Quantitative Measurements of HO2 and other products of n-butane oxidation (H2O2, H2O, CH2O, and C2H4) at elevated temperatures by direct coupling of a jet-stirred reactor with sampling nozzle and cavity ring-down spectroscopy (cw-CRDS).

For the first time quantitative measurements of the hydroperoxyl radical (HO2) in a jet-stirred reactor were performed thanks to a new experimental setup involving fast sampling and near-infrared cavity ring-down spectroscopy at low pressure. The experiments were performed at atmospheric pressure and over a range of temperatures (550-900 K) with n-butane, the simplest hydrocarbon fuel exhibiting cool flame oxidation chemistry which represents a key process for the auto-ignition in internal combustion engines. The same technique was also used to measure H2O2, H2O, CH2O, and C2H4 under the same conditions. This new setup brings new scientific horizons for characterizing complex reactive systems at elevated temperatures. Measuring HO2 formation from hydrocarbon oxidation is extremely important in determining the propensity of a fuel to follow chain-termination pathways from R + O2 compared to chain branching (leading to OH), helping to constrain and better validate detailed chemical kinetics models.