We explore the two-dimensional infrared response of D2O and of OD impurity at the interface of phospholipid membrane fragments. The spectra of the two aqueous states are inhomogeneously broadened due to the absorption of water molecule associated with the membrane interface in different structural sites. The nonlinear spectra of the two species allow disentangling of the spectral contributions of the aqueous states of two types: where the stretching modes are under effective mixing and where the stretching modes are uncoupled. By reviewing the results of the experimental studies with the support of molecular dynamic simulation we identify the spectral signatures of the main structural motives responsible for the inhomogeneous distribution of resonances in the infrared OD stretching region. Our analysis provides a quantitative estimate of the statistical population of the different aqueous species at the polar interface of the bilayer.