Soil Calcimetry Dynamics to Resolve Weathering Flux in Wollastonite-Amended Croplands

Enhanced Rock Weathering (ERW) is a promising carbon dioxide removal (CDR) strategy that accelerates mineral dissolution, sequestering atmospheric CO2 while improving soil health. This study builds on prior applications of soil calcimetry by investigating its ability to resolve short-term carbonate fluxes and rainfall-modulated weathering dynamics in wollastonite-amended croplands. Conducted over a single growing season (May–October 2024) in temperate row-crop fields near Port Colborne, Ontario—characterized by fibric mesisol soils (Histosols, FAO-WRB)—this study tests whether calcimetry can distinguish between dissolution and precipitation phases and serve as a proxy for weathering flux within the upper soil horizon, under the assumption that rapid pedogenic carbonate cycling dominates alkalinity retention in this soil–mineral system. Monthly measurements of soil pH (Milli-Q and CaCl2) and calcium carbonate equivalent (CCE) were conducted across 10 plots, totaling 180 composite samples. Results show significant alkalinization (p < 0.001), with average pH increases of ~+1.0 unit in both Milli-Q and CaCl2 extracts over the timeline. In contrast, CCE values showed high spatiotemporal variability (−2.5 to +6.4%) without consistent seasonal trends. The calcimetry-derived weathering proxy, log (Σ ΔCCE/Δt), correlated positively with pH (r = 0.652), capturing net carbonate accumulation, while the kinetic dissolution rate model correlated strongly and negatively with pH (r ≈ −1), reflecting acid-promoted dissolution. This divergence confirms that the two metrics capture complementary stages of the weathering–precipitation continuum. Rainfall strongly modulated short-term carbonate formation, with cumulative precipitation over the previous 7–10 days enhancing formation rates up to a saturation point (~30 mm), beyond which additional rainfall yielded diminishing returns. In contrast, dissolution fluxes remained largely independent of rainfall. These results highlight calcimetry as a direct, scalable, and dynamic tool not only for monitoring solid-phase carbonate formation, but also for inferring carbonate migration and dissolution dynamics. In systems dominated by rapid pedogenic carbonate cycling, this approach captures the majority of alkalinity fluxes, offering a conservative yet comprehensive proxy for CO2 sequestration.