Numerical Simulation of the Self‐Organizational Origin of Concentrically Zoned Aggregates of Siderite and Pyrite in Sediment‐Hosted Massive Sulfide Deposits

Abstract

AbstractConcentrically zoned pyrite aggregates (CZPA) are common in sediment‐hosted massive sulfide (SHMS) deposits and have been widely used to interpret the ore‐forming processes. There is considerable uncertainty, however, over the formation of aggregates that are oscillatorily zoned and contain randomly‐orientated pyrite microcrystals. Guided by the results of examination of the micro‐textures of CZPA and in‐situ chemical analyses, we conducted a quantitative diffusion‐reaction simulation to assess the mechanism of CZPA formation. Our study shows that oscillatory zoning results from the feedback between the diffusion of reactants and the nucleation‐growth of Fe‐sulfides. Externally derived Fe2+ diffuses into the early diagenetic sediments containing decomposing organic matter (2CH2O + SO42− = 2HCO3− + H2S) and reacts with H2S to form a pyrite layer via an intermediate pathway (Fe2+ + H2S → FeS + 2H+, FeS + H2S → FeS2 + H2). This growth of pyrite layers depletes the local concentration of reactants and suppresses nucleation until the diffusive reaction front advances and another layer is formed. Intermediate phases, for example, mackinawite, nucleate instead of pyrite, because of their greater ease of nucleation due to the low surface tension, and lead to the domination of nucleation over growth. The nucleation of mackinawite and occurrence of siderite in the CZPA are consistent with a low temperature, high pH, anoxic early diagenetic environment. Our study demonstrates that CZPA in SHMS deposits are formed by intrinsic self‐organizational processes rather than by extrinsic changes of ore‐forming fluids. The CZPA in SHMS deposits are thus indicative of their diagenetic origin with Fe2+ infiltrated and diffused from hydrothermal fluids into the sediments.