Source Quantification of South Asian Black Carbon Aerosols with Isotopes and Modeling.

Black carbon (BC) aerosols perturb climate and impoverish air quality/human health-affecting ∼1.5 billion people in South Asia. However, the lack of source-diagnostic observations of BC is hindering the evaluation of uncertain bottom-up emission inventories (EIs) and thereby also models/policies. Here, we present dual-isotope-based (Δ14C/δ13C) fingerprinting of wintertime BC at two receptor sites of the continental outflow. Our results show a remarkable similarity in contributions of biomass and fossil combustion, both from the site capturing the highly populated highly polluted Indo-Gangetic Plain footprint (IGP; Δ14C-fbiomass = 50 ± 3%) and the second site in the N. Indian Ocean representing a wider South Asian footprint (52 ± 6%). Yet, both sites reflect distinct δ13C-fingerprints, indicating a distinguishable contribution of C4-biomass burning from peninsular India (PI). Tailored-model-predicted season-averaged BC concentrations (700 ± 440 ng m-3) match observations (740 ± 250 ng m-3), however, unveiling a systematically increasing model-observation bias (+19% to -53%) through winter. Inclusion of BC from open burning alone does not reconcile predictions (fbiomass = 44 ± 8%) with observations. Direct source-segregated comparison reveals regional offsets in anthropogenic emission fluxes in EIs, overestimated fossil-BC in the IGP, and underestimated biomass-BC in PI, which contributes to the model-observation bias. This ground-truthing pinpoints uncertainties in BC emission sources, which benefit both climate/air-quality modeling and mitigation policies in South Asia.

Secondary Organic Aerosol Formation over Coastal Ocean: Inferences from Atmospheric Water-Soluble Low Molecular Weight Organic Compounds.

A lack of consensus on the distributions and formation pathways of secondary organic aerosols (SOA) over oceanic regions downwind of pollution sources limits our ability to assess their climate impact globally. As a case study, we report here on water-soluble SOA components such as dicarboxylic acids, oxocarboxylic acids, and α-dicarbonyls in the continental outflows from the Indo-Gangetic Plain (IGP) and Southeast Asia (SEA) to the Bay of Bengal. Oxalic acid (C2) is the dominant species followed by succinic (C4) and glyoxylic acids (ωC2) in the outflow. Nonsea-salt SO42- also dominates (∼70%) total water-soluble inorganic constituents and correlates well with aerosol liquid water content (LWC) and C2, indicating their production through aqueous phase photochemical reactions. Furthermore, mass ratios of dicarboxylic acids (C2/C4, C2/ωC2), and their relative abundances in water-soluble organic carbon and total organic carbon are quite similar between the two continental (IGP and SEA) outflows, indicating the formation of SOA through aqueous phase photochemical reactions in LWC-enriched aerosols, largely controlled by anthropogenic SO42-.

Link of the short-term temporal trends of Sr and Nd isotopic composition of aeolian dust over the Arabian Sea with the source emissions.

Aeolian transport of continental dust from the Middle East and South Asia to the Arabian Sea (AS) is an important route for delivering key trace metals and nutrients. Despite being surrounded by several deserts, it is not clear which dust source is most likely contributing to mineral aerosols over this marine basin in winter. Substantial information on dust source emissions and transport pathways over the AS is, thus, needed for better constraining the biogeochemical effects in the sunlit surface waters. Here, we investigated the Sr and Nd isotopic composition (87Sr/86Sr and εNd(0)), respectively) of dust samples collected over the AS during a GEOTRACES-India expedition (GI-10: 13 January-10 February 2020). Both tracers, 87Sr/86Sr (0.70957-0.72495) and εNd(0) (-24.0 to -9.3), showed pronounced spatial variability. These proxies were further tagged with their source profiles of surrounding land masses based on the origin of air mass back trajectories (AMBTs). We also encountered two dust storms (DS), one on 27 January 2020 (87Sr/86Sr: 0.70957; εNd(0): -9.3) and the second one on 10 February 2020 (87Sr/86Sr: 0.71474, εNd(0):-12.5), which showed distinct isotopic signatures. AMBTs and satellite imagery together revealed that DS1 is from the Arabian Peninsula and DS2 is from Iran and/or the Indo-Gangetic Plain. Notably, the Sr and Nd isotope composition of DS1 is further consistent with other dust samples collected over the pelagic waters, suggesting the impact of dust outbreaks from the Arabian Peninsula during winter season. Such documentation based on the 87Sr/86Sr and εNd(0) over the Arabian Sea, hitherto, is lacking in literature and, thus, highlights the need for more measurements.

Tracing the biomass burning emissions over the Arabian Sea in winter season: Implications from the molecular distributions and relative abundances of sugar compounds.

The widespread haze pollution over South Asia typically occurs in winter, affecting the abundance of organic aerosols (OA) over the Arabian Sea due to prevailing meteorology. We determined the concentrations of biomass burning (BB) derived anhydrosugars (levoglucosan: Lev, galactosan: Gal, and mannosan: Man), sugars (glucose, fructose, sucrose, and trehalose) and sugar alcohols (arabitol, mannitol, erythritol, and inositol) over the Arabian Sea during a winter cruise (6-24 December 2018). Molecular distributions revealed predominance of levoglucosan or sucrose. Besides, levoglucosan strongly correlated with mannosan, galactosan, sugar alcohols and elemental carbon, emphasizing their BB-origin. Backward air mass trajectories intercepted by the satellite-based fire counts over the Indo-Gangetic Plain together with relationship between stable carbon isotopic composition of TC (δ13CTC) and levoglucosan-C to organic carbon (%), confirmed the impact of BB-derived OA. A comparison of Lev/Man (av. 16.2) and Lev/K+ (av. 0.27) ratios over the Arabian Sea with the source-emissions revealed their origin from crop-residue burning. Rather high concentrations of Lev over the Arabian Sea compared to those documented over the Bay of Bengal, East China Sea, Sea of Japan and the western North Pacific further suggests a stronger impact of BB in the continental outflow over this marine basin. Besides, Lev/K+ ratios in marine aerosols exponentially decreased with an apparent increase in ambient relative humidity and temperature over the Arabian Sea during the South Asian outflow, implying a photochemical oxidation of BBOA. Such field-based relationship of Lev with the meteorological parameters can be useful for modelling the impact of BBOA on the surface Ocean. Besides, the aeolian input of sugar-C and water-soluble organic carbon (WSOC) accounted for 83 % and 92 % of that riverine supply to the Arabian Sea, respectively. This means atmospheric dry-deposition of sugars is an important external source of dissolved organic compounds to the surface water.

Unraveling the sources of atmospheric organic aerosols over the Arabian Sea: Insights from the stable carbon and nitrogen isotopic composition.

The isotopic composition of stable carbon (δ13C) and nitrogen (δ15N) in marine aerosols influenced by the continental outflows are useful proxies for understanding the aging and secondary formation processes. Every winter, the haze pollutants transported from South Asia significantly affect the chemical composition of marine atmospheric boundary layer of the Arabian Sea. Here, we assessed the δ13C of total carbon (TC) and δ15N of total nitrogen (TN) in marine aerosols collected over the Arabian Sea during a winter cruise (6-24 December 2018). TC (2.1-13.4 µg m-3) is strongly correlated with TN (0.9-5.0 µg m-3), likely because of their common source-emissions, biomass burning and fossil-fuel combustion in the Indo-Gangetic Plain and South Asia (corroborated by backward-air mass trajectories and satellite fire counts). Besides, the linear relationship between the mass ratios of water-soluble organic carbon (WSOC) to TC (0.04-0.65) and δ13CTC (-25.1‰ to -22.9‰) underscores the importance of aging process. This means oxidation of organic aerosols during transport not only influences the WSOC levels but also affects their δ13CTC. Likewise, the prevalent inverse linear relationship between the equivalent mass ratio of (NH4+/non-sea-salt- or nss-SO42-) and δ15NTN (+15.3‰ to +25.1‰) emphasizes the overall significance of neutralization reactions between major acidic ([nss-SO42-] ≫ [NO3-]) and alkaline species (NH4+) in aerosols. Higher δ15NTN values in winter than the spring inter-monsoon clearly emphasizes the significance of the anthropogenic combustion sources (i.e., biomass burning) in the South Asian outflow. A comparison of δ13CTC and δ15NTN with the source emissions revealed that crop-residue burning emissions followed by the coal fired power plants mostly dictate the atmospheric abundance of organic aerosols in the wider South Asian outflow.

Carbonaceous aerosols and their light absorption properties over the Bay of Bengal during continental outflow.

The marine atmosphere of the Bay of Bengal (BoB) is prone to get impacted by anthropogenic aerosols from the Indo-Gangetic Plain (IGP) and Southeast Asia (SEA), particularly during the northeast monsoon (NEM). In this study, we quantify and characterize carbonaceous aerosols and their absorption properties collected in two cruise campaigns onboard ORV Sindhu Sadhana during the continental outflow period over the BoB. Aerosol samples were classified based on the air mass back trajectory analyses, wherein samples were impacted by the continental air parcel (CAP), marine air parcel (MAP), and mix of both (CAP + MAP). Significant variability in the PM10 mass concentration (in µg m-3) is found with a maximum value for MAP samples (75.5 ± 36.4) followed by CAP + MAP (58.5 ± 27.3) and CAP (58.5 ± 27.3). The OC/EC ratio (>2) and diagnostic tracers i.e. nss-K+/EC (0.2-0.96) and nss-K+/OC (0.11-1.32) along with the absorption angstrom exponent (AAE: 4.31-6.02) and MODIS (Moderate Resolution Imaging Spectroradiometer) derived fire counts suggest the dominance of biomass burning emission sources. A positive correlation between OC and EC (i.e. r = 0.86, 0.70, and 0.42 for CAP, MAP, and CAP + MAP, respectively) further confirmed the similar emission sources of carbonaceous species. Similarly, a significant correlation between estimated secondary organic carbon (SOC) and water-soluble organic carbon (WSOC; r = 0.99, 0.96, and 0.97 for CAP, MAP, and CAP + MAP, respectively) indicate their similar chemical nature as well as dominant contribution of SOC to WSOC. The absorption coefficient (babs-365) and mass absorption efficiency (MAEBrC-365) of the soluble fraction were estimated at 365 nm wherein, babs-365 showed a linear relationship with WSOC and nss-K+, signifying the contribution of water soluble brown carbon from biomass burning emissions. The estimated MAEBrC-365 (0.30-0.93 m2 g-1), during this study, was consistent with the earlier observations over the BoB, particularly during the continental outflow season.

Large contribution of fossil-derived components to aqueous secondary organic aerosols in China.

Incomplete understanding of the sources of secondary organic aerosol (SOA) leads to large uncertainty in both air quality management and in climate change assessment. Chemical reactions occurring in the atmospheric aqueous phase represent an important source of SOA mass, yet, the effects of anthropogenic emissions on the aqueous SOA (aqSOA) are not well constrained. Here we use compound-specific dual-carbon isotopic fingerprints (δ13C and Δ14C) of dominant aqSOA molecules, such as oxalic acid, to track the precursor sources and formation mechanisms of aqSOA. Substantial stable carbon isotope fractionation of aqSOA molecules provides robust evidence for extensive aqueous-phase processing. Contrary to the paradigm that these aqSOA compounds are largely biogenic, radiocarbon-based source apportionments show that fossil precursors produced over one-half of the aqSOA molecules. Large fractions of fossil-derived aqSOA contribute substantially to the total water-soluble organic aerosol load and hence impact projections of both air quality and anthropogenic radiative forcing. Our findings reveal the importance of fossil emissions for aqSOA with effects on climate and air quality.

Low molecular weight dicarboxylic acids, oxocarboxylic acids and α-dicarbonyls as ozonolysis products of isoprene: Implication for the gaseous-phase formation of secondary organic aerosols.

Oxidation of isoprene, a major biogenic volatile organic compound emitted from forest canopies, is a potential source of oxalic acid; the dominant species in organic aerosols. We evaluated here ozonolysis of isoprene in dry darkness as a source of oxalic (C2), malonic (C3) and succinic (C4) acids. We found that oxalic acid and methylglyoxal are dominant products within 10 min of reaction followed by glyoxylic, malonic or succinic acids. Interestingly, molecular distributions of oxidation products from early reactions (9-29 min) were characterized by the predominance of methylglyoxal followed by C2, which became dominant after 30 min. The isoprene-derived secondary organic aerosols (SOAs) showed chemical evolution with reaction time towards the molecular characteristics of dicarboxylic acids similar to those of ambient aerosols (C2>C3≥C4). The carbon-based relative abundances of methylglyoxal decreased steadily (40%→30%), while those of C2 increased with reaction time (15%→25%), but no such variations persisted for glyoxal (6-10%). This finding means that methylglyoxal is more important intermediate of oxalic acid than glyoxal. In contrast, smaller variability and lower concentrations of pyruvic and glyoxylic acids than other intermediates indicate that oxalic acid formation under dry conditions follows a different pathway than in aqueous-phase heterogeneous chemistry usually invoked for cloud/fog/atmospheric waters. Here, we propose new reaction schemes for high levels of methylglyoxal and oxalic acid via gas-phase chemical reactions with ozone and OH radicals to better interpret the ambient SOA composition. Furthermore, the relative abundances of C2 exhibit small variability from 1 to 8 h, suggesting its stable character towards the oxidation by hydroxyl radicals.

Medical Oxygen Supply During COVID-19: A Study with Specific Reference to State of Andhra Pradesh, India.

Optimal medical infrastructure utilization became a high priority for Governments worldwide during the COVID-19 pandemic. Special attention is drawn to both the import and local manufacture of medical oxygen gas to ensure its uninterrupted supply to designated COVID-hospitals identified by the local administration. The paper apprises on the administrative and regulatory orders to control the supply and transportation of medical oxygen gas by examining its implementation in India in general and the State of Andhra Pradesh in particular. The paper enhances understanding of the working of governmental administrative systems amidst the emergency. The observations and findings from the research work can be vital inputs to Governmental institutions, regulatory bodies, the industry, and various other stakeholders dealing with medical oxygen gas so that policy and process flow can be improvised.

Evidence for brown carbon absorption over the Bay of Bengal during the southwest monsoon season: a possible oceanic source.

The near UV-visible light-absorbing organic carbon (OC) of ambient aerosols, referred to here as brown carbon (BrC), significantly influences the atmospheric radiative forcing on both regional and global scales. Here, we documented BrC absorption in the aqueous and methanol extracts of marine aerosols collected over the Bay of Bengal (BoB: September-October 2017) and a city, Visakhapatnam (May-June 2018), in southern India during the southwest monsoon (i.e., a transition period with weak continental impact). The absorption spectra of BrC over the BoB showed several peaks around 300-400 nm and differ from those observed over Visakhapatnam. The absorption coefficient of BrC over the BoB, unlike Visakhapatnam data, does not seem to covary with other chemical proxies of biomass burning (non-sea-salt or nss-K+) and coal combustion (nss-SO42-) in the continental outflows, suggesting a different source of BrC over the BoB. Besides, we observed higher proportions of water-insoluble organic carbon (WIOC/OC: 0.89 ± 0.02) and significant enrichment of Mg2+ over Na+ (i.e., relative to seawater) in BoB aerosols. This result and the backward air mass trajectories both hinted their major source of OC from marine-derived organic matter. In contrast, the absorption spectra of BrC over Visakhapatnam are like those from biomass burning emissions in the Indo-Gangetic Plain. This observation is further supported by the satellite-based fire counts and backward air mass trajectories. Therefore, our study underscores the BrC aerosols from the oceanic sources and southern India, hitherto unknown, and can improve our understanding of the regional climate effects of carbonaceous aerosols if included in models.

Brown carbon in the continental outflow to the North Indian Ocean.

In this paper, we synthesize the size distribution and optical properties of the atmospheric water-soluble fraction of light-absorbing organic carbon (brown carbon; BrC) in the continental outflow from the Indo-Gangetic Plain (IGP) in South Asia to the North Indian Ocean. A comparison of the mass absorption coefficient of water-soluble BrC (babs-WSBrC-365nm) in PM2.5 with that in PM10 sampled over the Bay of Bengal reveals the dominance of BrC in fine mode. Furthermore, the babs-BrC-365nm shows a significant linear relationship with mass concentrations of airborne particulate matter, water-soluble organic carbon and non-sea-salt-K+ in the continental outflow from the IGP. This observation emphasizes the ubiquitous nature and significant contribution of water-soluble BrC from biomass burning emissions (BBEs). Comparing the absorption properties from this study with global datasets, it is discernible that BBEs dominate BrC absorption. Furthermore, the imaginary refractive index of water-soluble BrC (kWSBrC-365nm) in marine aerosols sampled over the North Indian Ocean during November is significantly higher than during December to January. Thus, significant temporal variability is associated with crop-residue burning emissions in the IGP on the composition of BrC over the North Indian Ocean. Our estimates show that the babs-WSBrC-365nm and kWSBrC-365nm from post-harvest crop-residue burning emissions in the IGP are much higher than the BBEs from the southeastern United States and Amazonian forest fires. Another major finding of this study is the lack of significant relationship between kWSBrC-365nm and the mass ratio of elemental carbon to particulate organic matter, as previously suggested by chamber experiments to model varying BrC absorption properties in ambient aerosols. Therefore, considerable spatio-temporal variability prevails among emission sources (wood burning vs. crop-residue burning), which needs to be considered when assessing the regional radiative forcing of BrC relative to major absorbing elemental carbon.

Photochemical degradation affects the light absorption of water-soluble brown carbon in the South Asian outflow.

Light-absorbing organic aerosols, known as brown carbon (BrC), counteract the overall cooling effect of aerosols on Earth's climate. The spatial and temporal dynamics of their light-absorbing properties are poorly constrained and unaccounted for in climate models, because of limited ambient observations. We combine carbon isotope forensics (δ13C) with measurements of light absorption in a conceptual aging model to constrain the loss of light absorptivity (i.e., bleaching) of water-soluble BrC (WS-BrC) aerosols in one of the world's largest BrC emission regions-South Asia. On this regional scale, we find that atmospheric photochemical oxidation reduces the light absorption of WS-BrC by ~84% during transport over 6000 km in the Indo-Gangetic Plain, with an ambient first-order bleaching rate of 0.20 ± 0.05 day-1 during over-ocean transit across Bay of Bengal to an Indian Ocean receptor site. This study facilitates dynamic parameterization of WS-BrC absorption properties, thereby constraining BrC climate impact over South Asia.

Pyrogenic iron: The missing link to high iron solubility in aerosols.

Atmospheric deposition is a source of potentially bioavailable iron (Fe) and thus can partially control biological productivity in large parts of the ocean. However, the explanation of observed high aerosol Fe solubility compared to that in soil particles is still controversial, as several hypotheses have been proposed to explain this observation. Here, a statistical analysis of aerosol Fe solubility estimated from four models and observations compiled from multiple field campaigns suggests that pyrogenic aerosols are the main sources of aerosols with high Fe solubility at low concentration. Additionally, we find that field data over the Southern Ocean display a much wider range in aerosol Fe solubility compared to the models, which indicate an underestimation of labile Fe concentrations by a factor of 15. These findings suggest that pyrogenic Fe-containing aerosols are important sources of atmospheric bioavailable Fe to the open ocean and crucial for predicting anthropogenic perturbations to marine productivity.

Hygroscopic growth of particles nebulized from water-soluble extracts of PM2.5 aerosols over the Bay of Bengal: Influence of heterogeneity in air masses and formation pathways.

Hygroscopic properties of water-soluble matter (WSM) extracted from fine-mode aerosols (PM2.5) in the marine atmospheric boundary layer of the Bay of Bengal (BoB) have been investigated during a cruise from 27th December 2008 to 30th January 2009. Hygroscopic growth factors were measured on particles generated from the WSM using an H-TDMA system with an initial dry size of 100 nm in the range of 5-95% relative humidity (RH). The measured hygroscopic growth of WSM at 90% RH, g(90%)WSM, were ranged from 1.11 to 1.74 (mean: 1.43 ± 0.19) over the northern BoB and 1.12 to 1.38 (mean: 1.25 ± 0.09) over the southern BoB. A key finding is that distinct hygroscopic growth factors are associated with the air masses from the Indo-Gangetic plains (IGP), which are clearly distinguishable from those associated with air masses from Southeast Asia (SEA). We found higher (lower) g(90%)WSM over the northern (southern) BoB, which were associated with an IGP (SEA) air masses, probably due the formation of high hygroscopic salts such as (NH4)2SO4. On the other hand, biomass burning influenced SEA air masses confer the low hygroscopic salts such as K2SO4, MgSO4, and organic salts over the southern BoB. Interestingly, mass fractions of water-soluble organic matter (WSOM) showed negative and positive correlations with g(90%)WSM over the northern and southern BoB, respectively, suggesting that the mixing state of organic and inorganic fractions could play a major role on the g(90%)WSM over the BoB. Further, WSOM/SO4(2-) mass ratios suggest that SO4(2-) dominates the g(90%)WSM over the northern BoB whereas WSOM fractions were important over the southern BoB. The present study also suggests that aging process could significantly alter the hygroscopic growth of aerosol particles over the BoB, especially over the southern BoB.