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The environmentally-assisted fatigue crack growth behaviour of austenitic stainless steels in deoxygenated high temperature water at low strain rates has been reported to be greatly affected by the sulphur (S) content of the specimen, with high S specimens exhibiting significant reduced crack growth rates (retardation) when compared to low S specimens. To further the understanding of the mechanistic behaviour, fatigue crack growth experiments have been performed on high and low sulphur Type 316 austenitic stainless steel specimens tested in high temperature water and evaluated via microstructural characterisation techniques. At high strain rates the enhanced crack growth for both specimens appeared to be crystallographic and associated with slip localization. Furthermore, matching fracture surface analysis indicated discrepancy of the slip steps and micro-cleavage cracks between the matching surfaces, suggesting that slip steps and micro-cleavage cracking occurred after the crack-tip had advanced. It was also postulated that their formation may involve cathodically-produced hydrogen and shear deformation on the fracture surface. However, when the loading frequency was decreased, the high S specimens retarded the crack growth and the path was no longer crystallographic. Significant differences in the crack-tip opening displacements were observed in both materials, with blunt crack-tips in the high sulphur specimen and sharp tips in the low sulphur specimen when the strain rate was low. EBSD analysis at the crack-tips of both specimens showed that the strain was more localised at the crack-tip of the low sulphur specimen whist the strain ahead of the high sulphur specimen was more homogenous. It is thus postulated that retardation occurs when slip localisation is no longer the dominant factor. The localised deformation during enhancement is believed to have been caused by hydrogen enhanced localised plasticity (HELP) which causes the crack-tip to sharpen. The diffused strain distribution during crack growth retardation is believed to have been caused by hydrogen enhanced creep (HEC) which causes the crack-tip to blunt. It is also believed that both enhancement and retardation mechanisms are associated with contrasting effects deriving from hydrogen enhanced plasticity. Oxide induced crack closure was excluded as a mechanism responsible for retardation of fatigue crack growth when the stress ratio is high. Effects of hydrogen induced alpha' and ε martensite phases on oxidation behaviour of austenitic stainless steels in deoxygenated high temperature water have also been studied. Microstructural characterisation shows that hydrogen induced alpha' martensite enhances oxidation of austenitic stainless steels in deoxygenated high temperature water. The implications of this finding on environmentally assisted cracking of austenitic stainless steels in deoxygenated high temperature water is discussed.