The occurrence of As was studied in groundwater used for human consumption and irrigation, in stream water and sediments and in water from thermal springs in the drainage basin of Kalloni Gulf, island of Lesvos, Greece, in order to investigate the potential influence of the geothermal field of Polichnitos-Lisvori on the ground and surface water systems of the area. Total dissolved As varied in the range <0.7-88.3 microg L(-1) in groundwater, 41.1-90.7 microg L(-1) in thermal spring water and 0.4-13.2 microg L(-1) in stream water, whereas As concentrations in stream sediments varied between 2.0-21.9 mg kg(-1). Four out of 31 groundwater samples exceeded the EC standard of 10 microg L(-1). The survey revealed an enrichment in both surface and groundwater hydrological systems in the northern part of the area (average concentrations of As in groundwater, stream water and stream sediment: 8.0 microg L(-1), 8.8 microg L(-1) and 15.0 mg kg(-1) respectively), in association with the volcanic bedrocks, while lower As concentrations were found in the eastern part (average concentrations in groundwater, stream water and stream sediment: 2.9 microg L(-1), 1.7 microg L(-1) and 5.9 mg kg(-1) respectively), which is dominated by ophiolitic ultramafic formations. The variation of As levels between the different parts of the study area suggests that local geology exerts a determinant influence on As geochemical behaviour. On the other hand, the geothermal activity manifested in the area of Polichnitos-Lisvori does not affect the presence of As in groundwater and streams.