This study reports on fouling mechanisms of skim milk and whey during membrane distillation (MD) using polytetrafluoroethylene (PTFE) membranes. Structural and elemental changes along the fouling layer from the anchor point at the membrane to the top surface of the fouling layer have been investigated using synchrotron IR micro-spectroscopy and electron microscopy with associated energy dispersive X-ray spectroscopy (EDS). Initial adhesion of single components on a membrane representing a PTFE surface was observed in-situ utilizing reflectometry. Whey components were found to penetrate into the membrane matrix while skim milk fouling remained on top of the membrane. Whey proteins had weaker attractive interaction with the membrane and adhesion depended more on the presence of phosphorus near the membrane surface and throughout to establish the fouling layer. This work has given detailed insight into the fouling mechanisms of MD membranes in major dairy streams, essential for maintaining membrane distillation as operational for acceptable times, therewith allowing further development of this emerging technology. (c) 2013 Elsevier B.V. All rights reserved.