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The Buck Reef is a 250−400 m thick sequence of banded black and white (B&W) cherts deposited ca. 3416 Ma ago in a shallow basin. We provide field, petrological and geochemical constraints on the chert-forming process and the origin of the banding. White layers consist of nearly pure microquartz, while black layers are mixed with detrital carbonaceous matter, quartz grains and carbonaceous microlaminae, interpreted as remnants of microbial mats. The circulation of Si-rich fluid is recorded by abundant chert veins and pervasive silicification. However, the high purity of the white layers, their lack of internal structures and extremely low Al, Ti and high-field-strength elements preclude an origin by silicification of sedimentary or volcanic precursors. Moreover, their reworking at the surface into slab conglomerates, and sediment-like contacts with black layers rule out a diagenetic origin. We propose a new model whereby the white layers were periodically deposited as precipitates of pure silica; and the micro-layering within the black layers formed by annual temperature fluctuations, favouring microbial activity in summer and inorganic silica precipitation in winter. Outcrop-scale alternation of B&W layers was associated with major, thousand-year-long climate events: white cherts represent massive silica precipitation resulting from changes in ocean circulation and temperature during cold intervals.