The reaction rates of (CH3)(2)NNO and (CH3CH2)(2)NNO with NO3 radicals were determined relative to formaldehyde (CH2O) and ethene (CH2CH2) at 298 +/- 2 K and 1013 +/- 10 hPa in purified air by long path FTIR spectroscopy. The reactions are too slow to be of importance at atmospheric conditions: k(NO3+(CH3)2NNO) = (1.47 +/- 0.23) X 10(-16) and k(NO3+(CH3CH2)2NNO) = (5.1 0.4) X 10(-16) cm(3) molecule(-1) s(-1) (l sigma error limits). Theoretical calculations, based on CCSD-(T*)-F12a/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ, results, predict the corresponding imines as the sole primary products in nitrosamine reactions with NO3 and OH radicals.