Water oxygen partial pressure (PO2), pH, titration alkalinity (TA), temperature and salinity were measured hourly in rockpools during emersion periods occuring at various times of the diurnal cycle. Measurements allowed calculation of oxygen concentration (CO2), CO2 partial pressure (PCO2) and concentrations of bicarbonate, carbonate and total CO2 (CCO2). During night emersion periods, water PO2 decreased to almost zero in a few hours, pH fell, TA rose and PCO2 increased up to 1-3 Torr. During day emersion periods, water PO2 rose to 400-600 Torr, pH increased to more than 10, TA decreased substantially and PCO2 fell as low as 10(-4) Torr. The direction of the observed changes depended essentially on the illumination, indicating that respiratory and photosynthetic activities were the main processes involved. The large variations of the components of the carbonate system imply considerable changes of the CO2 capacitance coefficient in water, mainly during the day-time emersion. These changes are discussed in relation to the respiratory and acid-base physiology of the animals living in these biotopes.