An absolute rate pulse radiolysis technique was used to measure k(OH + 1,3-dioxolane) = (8.8 ± 0.9) × 10^-12 cm³ molecule^-1 s^-1 at 295 K in 1000 mbar of Ar. Relative rate techniques were used to study the reactions of OH radicals and Cl atoms with 1,3-dioxolane and Cl atoms with ethylene carbonate and methylene glycol diformate at 300 K in 1 bar of synthetic air. Rate coefficients were k(OH + 1,3-dioxolane) = (1.04 ± 0.16) × 10^-11, k(Cl + 1,3-dioxolane) = (1.6 ± 0.3) × 10^-10, k(Cl + ethylene carbonate) = (7.1 ± 1.7) × 10^-12, and k(Cl + methylene glycol diformate) = (5.6 ± 0.7) × 10^-13 cm³ molecule^-1 s^-1. OH radical and chlorine atom initiated oxidation of 1,3-dioxolane in 1 bar of N₂/O₂ mixtures at 298 K in the presence of NO_x gives ethylene carbonate and methylene glycol diformate. Molar yields of ethylene carbonate and methylene glycol diformate were 0.48 ± 0.07 and 0.50 ± 0.14 for OH radical initiation and 0.43 ± 0.07 and 0.53 ± 0.07 for Cl atom initiation. Product yields were independent of O₂ partial pressure over the range studied (60-800 mbar). A photochemical mechanism was developed to describe the OH-initiated degradation of 1,3-dioxolane in the presence of NO_x. The results are discussed with respect to the available literature data concerning the atmospheric chemistry of ethers.