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Summary Agriculture has claimed a large share of terrestrial environments in the tropics and subtropics through cultivation of native grasslands or forests. The impact of this anthropogenic change on speciation, dynamics, and ecological significance of sulphur (S) compounds is still poorly understood. We combined degradative wet-chemical reduction and S K-edge X-ray absorption near edge structure (XANES) spectroscopy techniques to evaluate the impact of long-term agricultural management of native grassland soils in South African Highveld on the amount, form and dynamics of S species. Sulphur XANES in the humic substances extracted by 0.1 m NaOH/0.4 m NaF solution showed the presence of strongly reduced (polysulphides, disulphides, thiols, monosulphides and thiophenes), intermediate (sulphoxides and sulphonates) and strongly oxidized (ester sulphates) organic-S. It showed that strongly oxidized-S is the predominant form (39–54%) of the total organic-S in the humic substances, and organic-S in the intermediate oxidation state represented 30–37% (78–93% of which was attributed to sulphonates). The strongly reduced organic-S comprised only 17–24% of the total organic-S. We did not find a close correlation between the results of a degradative wet-chemical procedure and XANES spectroscopy conducted in both the bulk soils (ester SO4-S from XANES versus HI-fractionation, r = 0.27; P < 0.05) and the humic substance extracts (ester SO4-S from XANES versus HI-fractionation, r= 0.39; P < 0.05). The ratio of reduced-S to strongly oxidized-S (R-S/O-S) in the humic substances decreased from 0.61 to 0.21, while the ratio of intermediate-S to strongly oxidized-S (I-S/O-S) declined from 0.93 to 0.61 after 90 years of arable cropping of the native grassland soils. Hence, there was a shift in oxidation state towards strongly oxidized-S (+6) and, thereby, a change in the relative proportion of the organic-S moieties associated with each oxidation state following cultivation of the native grassland soils. Therefore, we conclude that changes in land-use practice brought about not only quantitative change but also altered the composition of organic-S functional groups in these native subtropical grassland soils.