Factors and sources influencing ionic composition of atmospheric condensate during winter season in lower troposphere over Delhi, India

Atmospheric condensate (AC) and rainwater samples were collected during 2010–2011 winter season from Delhi and characterized for major cations and anions. The observed order of abundance of cations and anions in AC samples was NH ₄ ⁺ ?>?Ca²⁺?>?Na⁺?>?K⁺?>?Mg²⁺ and HCO ₃ ^? ?>?SO ₄ ^2? ?>?Cl^??>?NO ₂ ^? ?>?NO ₃ ^? ?>?F^?, respectively. All samples were alkaline in nature and Σ _cation/Σ _anion ratio was found to be close to one. NH ₄ ⁺ emissions followed by Ca²⁺ and Mg²⁺ were largely responsible for neutralization of acidity caused by high NO _x and SO₂ emissions from vehicles and thermal power plants in the region. Interestingly, AC samples show low nitrate content compared with its precursor nitrite, which is commonly reversed in case of rainwater. It could be due to (1) slow light-mediated oxidation of HONO; (2) larger emission of NO₂ and temperature inversion conditions entrapping them; and (3) formation and dissociation of ammonium nitrite, which seems to be possible as both carry close correlation in our data set. Principal component analysis indicated three factors (marine mixed with biomass burning, anthropogenic and terrestrial, and carbonates) for all ionic species. Significantly higher sulfate/nitrate ratio indicates greater anthropogenic contributions in AC samples compared with rainwater. Compared with rainwater, AC samples show higher abundance of all ionic species except SO₄, NO₃, and Ca suggesting inclusion of these ions by wash out process during rain events. Ionic composition and related variations in AC and rainwater samples indicate that two represent different processes in time and space coordinates. AC represents the near-surface interaction whereas rainwater chemistry is indicative of regional patterns. AC could be a suitable way to understand atmospheric water interactions with gas and solid particle species in the lower atmosphere.