The extracellular polymeric substances (EPS) extracted from four anaerobic granular sludges contain an important mineral fraction (20-77% of the EPS dry weight). The composition of the mineral fraction of EPS depends strongly of the extraction method applied and to a lesser extend of the origin of the anaerobic sludge. Centrifugation, sonication, and heating extraction procedures yield a similar mineral composition. However, extraction using a cationic exchange resin (CER) leads to an increase of the Na(+) content in the EPS extract because the CER promotes an exchange of divalent and trivalent inorganic elements in the EPS extracts toward Na(+). Chemical extraction protocols were also shown to contaminate the EPS extracts by impurities or carry over of the extractant itself (e.g., ethanol). A part of the mineral fraction is bound to the EPS organic matter and structures the EPS matrix in the granules. Scanning electron microscopic analysis (SEM-EDX) showed that, in addition, solid particles such as CaCO(3) and Ca(5)OH(PO(4))(3) containing various metallic elements (i.e., Al, Fe, Cu, Mn...) are present in the EPS as well. This inorganic fraction, too often neglected in EPS studies, can influence the physicochemical properties of EPS.