The Isua Supracrustal Belt, Greenland, of Early Archean age (3.81-3.70 Ga) represents the oldest crustal segment on Earth. Its complex lithology comprises an ophiolite-like unit and volcanic rocks reminiscent of boninites, which tie Isua supracrustals to an island arc environment. We here present zinc (Zn) isotope compositions measured on serpentinites and other rocks from the Isua supracrustal sequence and on serpentinites from modern ophiolites, midocean ridges, and the Mariana forearc. In stark contrast to modern midocean ridge and ophiolite serpentinites, Zn in Isua and Mariana serpentinites is markedly depleted in heavy isotopes with respect to the igneous average. Based on recent results of Zn isotope fractionation between coexisting species in solution, the Isua serpentinites were permeated by carbonate-rich, high-pH hydrothermal solutions at medium temperature (100-300°C). Zinc isotopes therefore stand out as a pH meter for fossil hydrothermal solutions. The geochemical features of the Isua fluids resemble the interstitial fluids sampled in the mud volcano serpentinites of the Mariana forearc. The reduced character and the high pH inferred for these fluids make Archean serpentine mud volcanoes a particularly favorable setting for the early stabilization of amino acids.hydrothermal fluids | serpentinization | origin of life | subduction zone T he discovery of oceanic black smokers and their unique fauna prompted the idea that life may have sprung from hydrothermal vent fields at the bottom of the ocean (1-3). The highly reducing conditions of the vent fields associated with midocean ridges fulfill one of the most stringent conditions for the stabilization of biomolecules. These conditions are a consequence of the metamorphic hydration and oxidation of ultramafic rocks of the oceanic lithosphere-a series of reactions known as serpentinization-that release highly reduced hydrothermal fluids with high concentrations of methane, ammonia, and hydrogen (4, 5). Serpentinization also produces FeNi 3 , which catalyses formation of complex organic compounds (5). Serpentinization thus provides both a source of reduced carbon and a potential energy source, which, together, create an environment suitable for the emergence of the first biomolecules. The vast majority of hydrothermal vent fields, however, especially those hosted by midocean ridges, spout solutions with pH well below the pK of amino acids, which makes them unsuitable for Strecker synthesis (6, 7). Attention therefore shifted toward high-pH hydrothermal vent sites (8, 9) and notably toward the modern vent fluids from the unusual midocean ridge locality of Lost City.The search for an Archean environment in which reducing and high-pH conditions coexist at temperatures appropriate for supporting early life prompted us to investigate Isua serpentinites and their associated hydrothermal carbonates (10). Precipitation of large amounts of carbonates suggests that carbonate ions were abundant in the parent fluid and therefore signals that the pH of this fluid was...