In many cases, when dealing with argillaceous fine-grained sedimentary rocks, the isotopic ages obtained from Rb–Sr whole-rock isochron calculations are of geological significance, despite the fact that the initial conditions of Sr isotopic homogenization are not fulfilled. To explain this, a mechanical mixing during deposition has been suggested, leading to an aggregate of mixed material with fairly uniform 87Sr/86Sr values, whatever Rb/Sr ratio is found in the analysed samples. This investigation of the behaviour of Rb and Sr during sedimentation and early diagenesis, involves study of more than 60 samples of fine-grained recent sediments from selected coastal localities of Brazil. The results indicate that pelitic samples from some recent to present-day transitional or shallow marine environments, such as the Jacarepaguá tidal flat and the Amazonas River mouth, where halmirolysis could have occurred, may produce nearly horizontal best-fit lines in a Rb–Sr isochron diagram. Moreover, the initial isotopic 87Sr/86Sr ratios appear to be well above 0.710. In open marine environments, such as the Campos Basin, where sampling was spread over more than 100 metres, exchanges between the argillaceous sediments and seawater potentially happen at low temperature, inducing a reduction of the 87Sr/86Sr isotopic composition of the sediments to nearly 0.710. An almost horizontal best-fit line is produced for the entire stratigraphic section, independent of the sedimentation age. We believe that in similar environments such ‘zero age isochrons’ are maintained for some time, testifying to exchanges between the sediment and the interstitial fluids, before the onset of burial diagenesis. The above described studies on fine-grained and recent argillaceous sediments seem to confirm the production of horizontal best-fit lines in isochron diagrams, justifying the application of the Rb–Sr whole-rock method to pelitic sedimentary rocks. The nature of the material is critical. The pelitic sediments to be analysed should contain only very limited amounts of coarse clastic material (especially feldspars and mica fragments) and consist mainly of fine clay minerals in which smectites, illite and mixed layers illite–smectite largely predominate.