Rate constants for the reactions of OH radicals with methyl N,N,N',N'-tetramethylphosphorodiamidate [CH3OP(O)[N(CH3)(2)](2); MTMPDA], ethyl N,N,N',N'-tetramethylphosphorodiamidate [C2H5OP(O)[N(CH3)(2)](2); ETMPDA], and O,S-dimethyl methylphosphonothioate [CH3OP(O)(CH3)SCH3; OSDMMP] have been measured over the temperature range 281-349 K at atmospheric pressure of air using a relative rate method. The rate expressions obtained were 4.96 X 10(-12) e((1058+/-71)/T) cm(3) molecule(-1) s(-1) (1.73 X 10(-1) cm(3) molecule(-1) s(-1) at 298 K) for OH + MTMPDA, 4.46 X 10(-12) e((1144+/-95)/T) cm(3) molecule(-1) s(-1) (2.07 x 10(-1) cm(3) molecule(-1) s(-1) at 298 K) for OH + ETMPDA, and 1.31 x 10(-13) e((1370+/-229)/T) cm(3) molecule(-1) s(-1) (1.30 X 10(-11) cm(3) molecule(-1) s(-1) at 298 K) for OH + OSDMMP. The rate constant for OH + OSDMMP was independent of O-2 content over the range 2.1-71% O-2 at 296 +/- 2 K. In addition, rate constants for the reactions of NO3 radicals and O-3 with MTMPDA, of (1.4 +/- 0.1) x 10(-12) cm(3) molecule(-1) s(-1) and <3.5 X 10(-19) cm(3) molecule(-1) s(-1), respectively, were measured at 297 +/- 2 K. Products of the OH radical- and, for MTMPDA, NO3 radical-initiated reactions were investigated using gas chromatography and in situ atmospheric pressure ionization mass spectrometry. A product of molecular weight 180 was observed from the OH and NO3 radical-initiated reactions of MTMPDA, and this is attributed to CH3OP(O)[N(CH3)(2)]N(CH3)CHO. Similarly, a product of molecular weight 194 was observed from the OH + ETMPDA reaction and attributed to C2H5OP(O)[N(CH3)(2)]N(CH3)CHO. Possible reaction mechanisms are discussed.