MOTIVATION: Analysis of metabolic networks through extreme rays such as extreme pathways and elementary flux modes has been shown to be effective for many applications. However, due to the combinatorial explosion of candidate vectors, their enumeration is currently limited to small- and medium-scale networks (typically <200 reactions). Partial enumeration of the extreme rays is shown to be possible, but either relies on generating them one-by-one or by implementing a sampling step in the enumeration algorithms. Sampling-based enumeration can be achieved through the canonical basis approach (CBA) or the nullspace approach (NSA). Both algorithms are very efficient in medium-scale networks, but struggle with elementarity testing in sampling-based enumeration of larger networks. RESULTS: In this paper, a novel elementarity test is defined and exploited, resulting in significant speedup of the enumeration. Even though NSA is currently considered more effective, the novel elementarity test allows CBA to significantly outpace NSA. This is shown through two case studies, ranging from a medium-scale network to a genome-scale metabolic network with over 600 reactions. In this study, extreme pathways are chosen as the extreme rays, but the novel elementarity test and CBA are equally applicable to the other types. With the increasing complexity of metabolic networks in recent years, CBA with the novel elementarity test shows even more promise as its advantages grows with increased network complexity. Given this scaling aspect, CBA is now the faster method for enumerating extreme rays in genome-scale metabolic networks. AVAILABILITY AND IMPLEMENTATION: All case studies are implemented in Python. The codebase used to generate extreme pathways using the different approaches is available at https://gitlab.kuleuven.be/biotec-plus/pos-def-ep.