Vertical distributions of the microscopic morphological characteristics and elemental composition of aerosols over India

Particle morphology and elemental compositions are among the crucial parameters of aerosols required for accurate understanding of the climatic effect of aerosols in the earth-atmosphere system; yet their vertical distributions and region specific properties are poorly characterised due to sparse in-situ measurements. This is the first study to classify and quantify the vertical distributions of the morphological characteristics and elemental composition of aerosols based on single particle as well as bulk chemical analysis over seven geographically diverse regions of northern and central parts of India during spring (April-May, 2013), carried out as a part of Regional Aerosol Warming Experiment (RAWEX). Significant regional distinctiveness in shapes (non-sphericity), sizes and elemental compositions of the airborne particles were conspicuous, having dominance of highly irregular granular aggregates over the north Indian sites. The non-spherical coarse mode particles dominated the lower free tropospheric regions (> 2 km) of the Indo-Gangetic Plains (IGP). These particles could be responsible for enhanced spring time aerosol absorption in the elevated region of the atmosphere. Elemental compositions of the single particle analysis indicate that the free tropospheric layer over the IGP and central India is enriched with Na and Ca compounds mixed with Fe or Al (soil particles), indicating long range transport of crustal aerosols. This finding is very well supported by the bulk particle analysis indicating abundance of Ca(2+)in the free troposphere with low contribution of ssNa(+). Particles with irregular rough surfaces having dominance of SiO(2)were observed over all the study sites. The percentage share of spherical (either smooth or rough) particles to the total morphological characteristics of the particles was found to be highly subdued (<10%). The present study thus critically assesses the relevant knowledge pertaining to the morphological features of aerosols over the IGP during spring for the accurate estimation of aerosol radiative properties. More such efforts are required in future to study the connections and dependencies between morphological and radiative properties of aerosols in different seasons.Peer reviewe

An evaluation of new particle formation events in Helsinki during a Baltic Sea cyanobacterial summer bloom

Several studies have investigated new particle formation (NPF) events from various sites ranging from pristine locations, including forest sites, to urban areas. However, there is still a dearth of studies investigating NPF processes and subsequent aerosol growth in coastal yet semi-urban sites, where the tropospheric layer is a concoction of biogenic and anthropogenic gases and particles. The investigation of factors leading to NPF becomes extremely complex due to the highly dynamic meteorological conditions at the coastline especially when combined with both continental and oceanic weather conditions. Herein, we engage in a comprehensive study of particle number size distributions and aerosol-forming precursor vapors at the coastal semi-urban site in Helsinki, Finland. The measurement period, 25 June-18 August 2019, was timed with the recurring cyanobacterial summer bloom in the Baltic Sea region and coastal regions of Finland. Our study recorded several regional/local NPF and aerosol burst events during this period. Although the overall anthropogenic influence on sulfuric acid (SA) concentrations was low during the measurement period, we observed that the regional or local NPF events, characterized by SA concentrations on the order of 10(7) molec. cm(-3), occurred mostly when the air mass traveled over the land areas. Interestingly, when the air mass traveled over the Baltic Sea, an area enriched with algae and cyanobacterial blooms, high iodic acid (IA) concentration coincided with an aerosol burst or a spike event at the measurement site. Further, SA-rich bursts were seen when the air mass traveled over the Gulf of Bothnia, enriched with cyanobacterial blooms. The two most important factors affecting aerosol precursor vapor concentrations, and thus the aerosol formation, were speculated to be (1) the type of phytoplankton species and intensity of bloom present in the coastal regions of Finland and the Baltic Sea and (2) the wind direction. During the events, most of the growth of sub-3 nm particles was probably due to SA, rather than IA or methane sulfonic acid (MSA); however much of the particle growth remained unexplained indicative of the strong role of organics in the growth of particles, especially in the 3-7 nm particle size range. Further studies are needed to explore the role of organics in NPF events and the potential influence of cyanobacterial blooms in coastal locations.Peer reviewe

Sources and sinks driving sulfuric acid concentrations in contrasting environments : implications on proxy calculations

Sulfuric acid has been shown to be a key driver for new particle formation and subsequent growth in various environments, mainly due to its low volatility. However, direct measurements of gas-phase sulfuric acid are oftentimes not available, and the current sulfuric acid proxies cannot predict, for example, its nighttime concentrations or result in significant discrepancies with measured values. Here, we define the sources and sinks of sulfuric acid in different environments and derive a new physical proxy for sulfuric acid to be utilized in locations and during periods when it is not measured. We used H2SO4 measurements from four different locations: Hyytiala, Finland; Agia Marina, Cyprus; Budapest, Hungary; and Beijing, China, representing semi-pristine boreal forest, rural environment in the Mediterranean area, urban environment and heavily polluted megacity, respectively. The new proxy takes into account the formation of sulfuric acid from SO2 via OH oxidation and other oxidation pathways, specifically via stabilized Criegee intermediates. The sulfuric acid sinks included in the proxy are its condensation sink (CS) and atmospheric clustering starting from H2SO4 dimer formation. Indeed, we found that the observed sulfuric acid concentration can be explained by the proposed sources and sinks with similar coefficients in the four contrasting environments where we have tested it. Thus, the new proxy is a more flexible and an important improvement over previous proxies. Following the recommendations in this paper, a proxy for a specific location can be derived.Peer reviewe

Role of iodine oxoacids in atmospheric aerosol nucleation

Iodic acid (HIO3) is known to form aerosol particles in coastal marine regions, but predicted nucleation and growth rates are lacking. Using the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber, we find that the nucleation rates of HIO3 particles are rapid, even exceeding sulfuric acid-ammonia rates under similar conditions. We also find that ion-induced nucleation involves IO3- and the sequential addition of HIO3 and that it proceeds at the kinetic limit below +10 degrees C. In contrast, neutral nucleation involves the repeated sequential addition of iodous acid (HIO2) followed by HIO3, showing that HIO2 plays a key stabilizing role. Freshly formed particles are composed almost entirely of HIO3, which drives rapid particle growth at the kinetic limit. Our measurements indicate that iodine oxoacid particle formation can compete with sulfuric acid in pristine regions of the atmosphere.Peer reviewe

Direct field evidence of autocatalytic iodine release from atmospheric aerosol

Reactive iodine plays a key role in determining the oxidation capacity, or cleansing capacity, of the atmosphere in addition to being implicated in the formation of new particles in the marine boundary layer. The postulation that heterogeneous cycling of reactive iodine on aerosols may significantly influence the lifetime of ozone in the troposphere not only remains poorly understood but also heretofore has never been observed or quantified in the field. Here, we report direct ambient observations of hypoiodous acid (HOI) and heterogeneous recycling of interhalogen product species (i.e., iodine monochloride [ICI] and iodine monobromide [IBr]) in a midlatitude coastal environment. Significant levels of ICI and IBr with mean daily maxima of 4.3 and 3.0 parts per trillion by volume (1-min average), respectively, have been observed throughout the campaign. We show that the heterogeneous reaction of HOI on marine aerosol and subsequent production of iodine interhalogens are much faster than previously thought. These results indicate that the fast formation of iodine interhalogens, together with their rapid photolysis, results in more efficient recycling of atomic iodine than currently considered in models. Photolysis of the observed ICI and IBr leads to a 32% increase in the daytime average of atomic iodine production rate, thereby enhancing the average daytime iodine-catalyzed ozone loss rate by 10 to 20%. Our findings provide direct field evidence that the autocatalytic mechanism of iodine release from marine aerosol is important in the atmosphere and can have significant impacts on atmospheric oxidation capacity.Peer reviewe

Role of iodine oxoacids in atmospheric aerosol nucleation

Iodic acid (HIO₃) is known to form aerosol particles in coastal marine regions, but predicted nucleation and growth rates are lacking. Using the CERN CLOUD (Cosmics Leaving Outdoor Droplets) chamber, we find that the nucleation rates of HIO₃ particles are rapid, even exceeding sulfuric acid–ammonia rates under similar conditions. We also find that ion-induced nucleation involves IO₃⁻ and the sequential addition of HIO₃ and that it proceeds at the kinetic limit below +10°C. In contrast, neutral nucleation involves the repeated sequential addition of iodous acid (HIO₂) followed by HIO₃, showing that HIO₂ plays a key stabilizing role. Freshly formed particles are composed almost entirely of HIO₃, which drives rapid particle growth at the kinetic limit. Our measurements indicate that iodine oxoacid particle formation can compete with sulfuric acid in pristine regions of the atmosphere

Multi-layer distribution of Black Carbon and Inorganic Ions in the Snow-packs of western Himalayas and Snow Albedo Forcing

The plausible impact of light-absorbing aerosols on snow darkening and subsequent retreating of glaciers is a global climatic concern. In this study, we present the characteristics of multi-layer distribution and effects of Black Carbon (BC) and inorganic ions in the snowpacks of Khardung (KG) and Phuche (PG) glaciers (> 5 km a.s.l.) in the western Himalayas. We observed significant vertical heterogeneity of BC in the snowpacks of KG (-42-428 ng g-1) and PG (-59 and 299 ng g-1), with higher concentrations in aged snow. Similar to BC, ions in the multi-layer snowpack also depicted prominent vertical heterogeneity with strong crustal influence (as indicated by abundant nssCa2+) in the aged snow layers of KG, which also possess a higher snow-melt rate as compared to PG. Among the other inorganic ions, the vertical profiles of nssSO42- and NO3- indicated elution and refreezing effects. The computation of the effective snow albedo for different snow-darkening and snow-physical processes vindicated the need of considering the multilayer model for the accurate quantification of effects of heterogeneous distributions of light absorbing aerosols (LAA) in the snowpacks. Following this, the multi-layer simulations of snow-albedo in the SNICAR model demonstrated the change in snow albedo by 2.5-9.0% for the amount of LAA observed in our study. This resulted in snow albedo forcing of 49.2 Wm-2 for PG, 30.8 Wm-2 for KG1 and 29.6 Wm-2 for KG2 for the typical snow-physical properties in the study region. Comprehensive data sets comprising physical, morphological and chemical properties of aerosols and snow are imperative to predict aerosol-induced snow darkening and the associated anomalous melting of snow/glacier over the Himalayan region.Peer reviewe

Aerosol black carbon over Svalbard regions of Arctic

In view of the climate impact of aerosol Black Carbon (BC) over snow covered regions (through enhanced absorption of radiation as well as snow-albedo forcing), and in view of the increasing anthropogenic presence and influence in the northern polar regions, continuous long term measurements of airborne BC have been undertaken from the Svalbard region of Norwegian Arctic (Ny-Ålesund, 79°N, 12°E, 8 m a.s.l.). This study, employing data over a period of 4-years (2010–2013) have shown a consistent spring-time enhancement in BC concentrations, having a (climatological) seasonal mean value of ∼50.3 ± 19.5 ng m−3, nearly 3-times higher than the lowest BC concentrations in summer (∼19.5 ± 6.5 ng m−3). Spectral variation of absorbance indicates that long-range transported biomass burning aerosols contribute as high as 25% to the high BC concentrations in the Arctic atmosphere in spring. Concurrent estimates of BC concentrations in the Arctic snow (for an ensemble of snow samples collected over a period of time during spring) showed values ranging from 0.6 ppb to 4.1 ppb. These values have been used to estimate the BC scavenging ratio (SR). Our studies revealed a mean value of SR∼98 ± 46, which varied over wide range from 40 to 184 for individual samples. In a broader perspective, the seasonal variations of atmospheric BC concentrations at the Arctic are similar to those seen at the high altitude Himalayas; even though the concentrations are much lower at Arctic. It is found that synoptic conditions mainly influence the high altitude Himalayas, while the influences of local anthropogenic influences are not negligible at the Arctic in modulating the seasonal variations of absorbing aerosols

Widespread detection of chlorine oxyacids in the Arctic atmosphere

Observations are reported of HClO3 and HClO4 in the atmosphere and their widespread occurrence over the pan-Arctic during spring, providing further insights into atmospheric chlorine cycling in the polar environment.Chlorine radicals are strong atmospheric oxidants known to play an important role in the depletion of surface ozone and the degradation of methane in the Arctic troposphere. Initial oxidation processes of chlorine produce chlorine oxides, and it has been speculated that the final oxidation steps lead to the formation of chloric (HClO3) and perchloric (HClO4) acids, although these two species have not been detected in the atmosphere. Here, we present atmospheric observations of gas-phase HClO3 and HClO4. Significant levels of HClO3 were observed during springtime at Greenland (Villum Research Station), Ny-angstrom lesund research station and over the central Arctic Ocean, on-board research vessel Polarstern during the Multidisciplinary drifting Observatory for the Study of the Arctic Climate (MOSAiC) campaign, with estimated concentrations up to 7 x 10(6) molecule cm(-3). The increase in HClO3, concomitantly with that in HClO4, was linked to the increase in bromine levels. These observations indicated that bromine chemistry enhances the formation of OClO, which is subsequently oxidized into HClO3 and HClO4 by hydroxyl radicals. HClO3 and HClO4 are not photoactive and therefore their loss through heterogeneous uptake on aerosol and snow surfaces can function as a previously missing atmospheric sink for reactive chlorine, thereby reducing the chlorine-driven oxidation capacity in the Arctic boundary layer. Our study reveals additional chlorine species in the atmosphere, providing further insights into atmospheric chlorine cycling in the polar environment.Peer reviewe