Coal ball formation and a soil extinction near the P-Tr boundary

Coal balls are calcium carbonate accumulations that commonly permineralize paleotropical PermoCarboniferous coal deposits and preserve exceptional specimens of the coal swamp flora. A widely applicable model for the origin of coal balls is lacking despite the study of these deposits for over a century. Two characteristics of coal balls have been particularly challenging to explain: 1) their temporal range is restricted to the PermoCarboniferous and 2) their typical oxygen isotope and elemental compositions paradoxically indicate freshwater and marine origins, respectively. We propose a new model for coal ball formation. The first step in our model is the episodic delivery of seawater and marine carbonate sediment to coastal mires. Next, these waters are diluted by freshwater and the carbonates dissolve at the elevated pCO2 of the mire subsurface. Finally, as waters flow laterally through stands of arborescent lycopsids, aqueous CO2 in the pore spaces of the peat escapes by diffusion through the air-filled lycopsid rootlets into the overlying water column, where some rootlets are thought to have extended. The CO2 escape drives calcite precipitation in the soil zone. This model explains the narrow temporal occurrence of coal balls, which coincides with the peak diversity of arborescent lycopsids. It also resolves the geochemical conundrum; dilution by freshwater can result in relatively low pore water δ18O values without preventing high-Mg calcite formation. Furthermore, we show mathematically that for published densities of arborescent lycopsid root mats and for reasonable rates of lateral water flow and vertical peat accumulation, CO2 could escape rapidly enough through the rootlets to fill >35% of the porosity with calcite before substantial burial (top several decimeters of peat), explaining the exceptional preservation of coal swamp flora. Therefore, we suggest that coal balls are pedogenic in origin and that their disappearance from the rock record represents the first documented soil extinction on a vegetated planet.