Organic-rich shales exhibit a wide range of vanadium (V) concentrations in deep-time successions. Although V accumulation is generally acknowledged to be related to redox state, organic matter and clay mineral content, previous studies have failed to explain the mechanism of variable V enrichment in organic-rich shales. Here, we hypothesize that clay-organic nanocomposites control authigenic V uptake in organic-rich shales. Specifically, V is scavenged by dissolved organic matter in seawater, which is then taken up by smectite during transport or deposition, followed by V incorporation into illite through illitization of smectite and pyrolysis of organic matter during diagenesis. To test this hypothesis, lower Cambrian black shales from South China were investigated by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) at a micro- and nanoscale. Results show that only 1M/1M(d)-type illite, generated through transformation from a smectite precursor, has significant V concentrations (0.7-4.8 wt%), whereas 2M1-type illite and other minerals contain little or no V. All 1M/1M(d)-type illite was closely associated with organic matter, occurring as clay-organic nanocomposites. Our results are significant in (i) showing clay-organic nanocomposites play a key role in V cycling in the marine system, (ii) providing a mechanism for understanding variations in the V concentrations of deep-time organic-rich shales, and (iii) improving strategies for prospecting and extraction of V ores.

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