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One of the primary contributors to this distincitive smell is the bicyclic organic compound shown here, geosmin. According to Wikipedia, it is produced by a number of soil bacteria such as the Actinomycetes (which also have a variety of biotechnological uses), and is also responsible for the earthy taste of beets and bottom-dwelling freshwater fish. The human nose can detect geosmin at vanishingly low parts-per-trillion concentrations.
Ahhh... the sweet smell of microbial metabolic biochemistry.
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