In this study the frequency of days with extreme low (termed ELOs) and extreme high (termed EHOs) total ozone values and their influence on mean values and trends are analyzed for the world's longest total ozone record (Arosa, Switzerland). The results show (i) an increase in ELOs and (ii) a decrease in EHOs during the last decades and (iii) that the overall trend during the 1970s and 1980s in total ozone is strongly dominated by changes in these extreme events. After removing the extremes, the time series shows a strongly reduced trend (reduction by a factor of 2.5 for trend in annual mean). Excursions in the frequency of extreme events reveal "fingerprints" of dynamical factors such as ENSO or NAO, and chemical factors, such as cold Arctic vortex ozone losses, as well as major volcanic eruptions of the 20th century (Gunung Agung, El Chichón, Mt. Pinatubo). Furthermore, atmospheric loading of ozone depleting substances leads to a continuous modification of column ozone in the Northern Hemisphere also with respect to extreme values (partly again in connection with polar vortex contributions). Application of extreme value theory allows the identification of many more such "fingerprints" than conventional time series analysis of annual and seasonal mean values. The analysis shows in particular the strong influence of dynamics, revealing that even moderate ENSO and NAO events have a discernible effect on total ozone. Overall the approach to extremal modelling provides new information on time series properties, variability, trends and the influence of dynamics and chemistry, complementing earlier analyses focusing only on monthly (or annual) mean values.