The structure and permeability of cementum are changed during the course of periodontal disease. In this study, the transport of water-soluble, spin-labelled molecules through cementum was studied by electron paramagnetic resonance (EPR). Cementum samples cut from different parts of the root were classified into four different groups: (A) samples exposed to the oral environment, (B) samples exposed to the periodontal-pocket environment; (C) samples cut from periodontally involved teeth but not exposed to saliva or periodontal pocket and (D) samples from sound young teeth extracted for orthodontic reasons. In order to obtain undamaged cementum, a dentine layer was left on each sample. Two methods were used to measure the diffusion coefficients of spin-labelled molecules in cementum dentine samples. First, the method of one-dimensional EPR imaging (EPRI) was used to evaluate the penetration of spin-labelled molecules into the cementum/dentine structure. Second, the diaphragm-cell method was used to determine the diffusion coefficients of the labelled molecules through the cementum under steady-state conditions. The results indicate that the interface between cementum and dentine is a barrier to diffusion. A set of diffusion (D) and partition (K) coefficients to describe the molecular transport in cementum, barrier and dentine was generated from the experimental data of both methods. For cementum (c), the barrier (b) and dentine (d) these coefficients were: Dc= 10(-8)cm2/s, Db= 10(-10)cm2/s, Dd= 10(-6)cm2/s and K=0.1. For the particular periodontally involved and uninvolved teeth the value of the rate-limiting barrier was DbA= 0.3 +/- 0.03 x 10(-10)cm2/s, DbB= 1 +/-0.3 x 10(-10)cm2/s, DbC= 0.3 +/- 0.03 x 10(-10)cm2/s, DbD= 0.4 +/- 0.05 x 10(-10)cm2/s. The largest diffusion flux across the dental hard tissue was found in the samples that had been exposed to the pocket environment (3.1 +/- 0.2) x 10(-9)cm2/s (p < 0.01), which coincided with the permeability calculated from the data evaluated by EPRI. The transport of the labelled molecules into and through the cementum dentine samples depends on the structure of the dental hard tissues, which changes during the course of periodontal disease. Knowledge of molecular diffusion across the tooth cementum/dentine structure is likely to be important for planning new treatments for periodontal disease.