ABSTRACT
Elucidating isotope exchange between atmospheric trace molecular species is important for environment monitoring, climate control studies, and a fundamental understanding of atmospheric chemistry. Here, we provide direct experimental evidence of oxygen-isotopic exchange between carbon dioxide (CO2) and nitrogen dioxide (NO2), which are simultaneously emitted into the atmosphere from common sources. A combined near-infrared and UV-vis optical cavity-enhanced experimental investigation along with quantum-chemical calculations followed by a reaction modeling study revealed that CO2 and NO2 can communicate isotopically by near-ultraviolet-driven NO2 photolysis. Our results found evidence for a near-barrierless (1.67 kcal/mol) nitrate-containing complex having a very short lifetime (â¼13 ns) which facilitates the transfer of 18O-isotopes from 18O12C16O to N16O16O, leading to isotopic depletion of 18O in 18O12C16O, thus opening a new gas-phase isotope-selective chemical transformation mechanism in the lower atmosphere. This isotope exchange study may serve as a new window into the fundamental understanding of isotopic photochemistry, oxygen isotopic fractionations, and climate modeling.
ABSTRACT
Forward scattering is an essential tool for investigating the colloidal suspension of polystyrene microspheres (PSMs). Evanescent wave coupled cavity ringdown spectroscopy (EW-CRDS) shows the anomalous extinction behavior in the limit of PSM particles that is much larger than the wavelength. EW-CRDS is a highly sensitive technique that improves weak absorption signals by enhancing the absorption path length, allowing for probing a range of processes at the solid/liquid interface by assessing the extinction properties. Additionally, it possesses the ability to sense a minimum absorbance of 1.2 × 10-6. EW-CRDS provides sufficient accuracy to detect correlation effects for PSMs in water at the interfacial region and their influence on forward scattering or extinction. In this work, we discuss the impact of volume fraction on the extinction of scatterers composed of microparticles in aqueous media. The findings of this study will contribute to a deeper understanding of the scattering dynamics in colloidal suspensions, with potential applications in various fields, including biology and metrology.
