Petrographic and calcrete carbon isotope data from seasonally waterlogged Upper Silurian (Přídolí) to Lower Devonian (Pragian) palaeo-Vertisols of the Old Red Sandstone, South Wales, UK, are presented. The δ 13 C values mostly range from −9 to −12‰ (VPDB), suggesting that the soils were inhabited by abundant vegetation that when oxidized (perhaps with microbial assistance) resulted in CO 2 -rich soils. Such soils would favour calcrete precipitation through equilibration of soil zone CO 2 with the relatively lower atmospheric pCO 2 . However, reliably estimating palaeoatmospheric pCO 2 using these carbon isotope data is a challenge.