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Large volumes of crude oil accidentally released into the sea may cause irreversible adverse impacts on marine and coastal environments. Large swath optical imagery, acquired using platforms such as the moderate-resolution imaging spectroradiometer (MODIS), is frequently used for massive oil spill detection, attributing to its large coverage and short global revisit, providing rich data for oil spill monitoring. The aim of this study was to develop a suitable approach for massive oil spill detection in sun glint optical imagery. Specifically, preprocessing procedures were conducted to mitigate the inhomogeneous light field over the spilled area caused by sun glint, enhance the target boundary contrast, and maintain the internal homogeneity within the target. The image was then segmented into super-pixels based on a simple linear clustering method with similar characteristics of color, brightness, and texture. The neighborhood super-pixels were merged into target objects through the region adjacency graph method based on the Euclidean distance of their colors with an adaptive termination threshold. Oil slicks from the generated bright/dark objects were discriminated through a decision tree with parameters based on spectral and spatial characteristics. The proposed approach was applied to oil spill detection in MODIS images acquired during the Montara oil spill in 2009, with an overall extraction precision of 0.8, recall of 0.838, and F1-score of 0.818. Such an approach is expected to provide timely and accurate oil spill detection for disaster emergency response and ecological impact assessment. Full article