Abstract: The refining of silver ores in New Spain was defined by the chemical nature of the silver ore. Argentiferous galena (lead sulphide) could only be refined by smelting (36% silver produced), irrespective of silver content, and amalgamation (64%) could only be applied to the silver sulphide ores. Both processes were transferred from Europe, but amalgamation was transformed by local expertise from a recipe of limited application to an industrial-scale solution for refining sulphidic silver ores. Its implementation shaped the environmental history of colonial silver refining in the New World. Mercury was consumed mainly through its chemical conversion into calomel, with minimal emissions of volatile mercury. Waste silt and liquid mercury in the soil and waterways were its main legacy. Smelting created a greater impact on the environment of New Spain, via lead in lead fumes as the main heavy metal issued to the air, and its depletion of woodlands. This article argues that a technical analysis of period refining practices in New Spain reorients our understanding of Spain's imperial relations with its New World colonies, of the role of local knowledge in a global economy of silver production, and of environmental issues in colonial history. It thus speaks to the problem of unpacking the complex web of relations that composed early European imperialism, in which were enmeshed commodities such as silver, cotton and sugar.