Soils initially contaminated with 36Cl in the chloride form were subjected to solid-liquid extractions using a variety of reagents including deionised water and 1 M sodium hydroxide (NaOH). 1 M NaOH was found to result in the greatest recovery of 36Cl from the soils, a result which provided initial evidence that radioactive chlorine became attached to humic substances present naturally within the soils. Deionised water and 1 M NaOH extracts were subjected to analysis involving separation by gel filtration chromatography (GFC). It was found that 36Cl in 1 M NaOH extracts associated preferentially with low molecular weight (LMW) fractions of humic substances whereas, in deionised water extracts, 36Cl appeared to be present exclusively in the chloride form. Previous literature evidence, mainly from highly organic forest soils, suggests that conversion of stable chlorine from chloride to organic forms can occur as a result of biological action. The present paper also presents good evidence for the specific attachment of stable chlorine (37Cl) to a LMW humic fraction, again demonstrated using GFC separation. Current risk assessments of the deep geological disposal of solid radioactive wastes containing 36Cl typically assume a very low degree of sorption based on the notion that the predominant environmental species of radiochlorine is chloride. This paper concludes with a brief discussion on the implications of organochlorine formation in the biosphere for assessment of the radiological impact of deep geological disposal of solid radioactive wastes.