Abstract. Myriad studies have shown the extent of human alteration to global biogeochemical cycles. Yet, there is only a limited understanding of the influence that humans have over silicate weathering fluxes; fluxes that have regulated atmospheric carbon dioxide concentrations and global climate over geologic timescales. Natural landscapes have been reshaped into agricultural ones to meet food needs for growing world populations. These processes modify soil properties, alter hydrology, affect erosion, and consequently impact water-soil-rock interactions such as chemical weathering. Dissolved silica (DSi), Ca2+, Mg2+, NO3–, and total alkalinity were measured in water samples collected from five small (0.0065 to 0.383 km2) gauged watersheds at the North Appalachian Experimental Watershed (NAEW) near Coshocton, Ohio, USA. The sampled watersheds in this unglaciated region include: a forested site (70+ year stand), mixed agricultural use (corn, forest, pasture), an unimproved pasture, tilled corn, and a recently (<3 yr) converted no-till corn field. The first three watersheds had perennial streams, but the two corn watersheds only produced runoff during storms and snowmelt. For the perennial streams, total discharge was an important control of dissolved silicate transport. Median DSi yields (2210–3080 kg km−2 yr–1) were similar to the median of annual averages between 1979–2009 for the much larger Ohio-Tennessee River Basin (2560 kg km−2 yr–1). Corn watersheds, which only had surface runoff, had substantially lower DSi yields (<530 kg km−2 yr–1) than the perennial-flow watersheds. The lack of contributions from Si-enriched groundwater largely explained their much lower DSi yields with respect to sites having baseflow. A significant positive correlation between the molar ratio of (Ca2++Mg2+)/alkalinity to DSi in the tilled corn and the forested site suggested, however, that silicate minerals weathered as alkalinity was lost via enhanced nitrification resulting from fertilizer additions to the corn watershed and from leaf litter decomposition in the forest. This same relation was observed in the Ohio-Tennessee River Basin where dominant landuse types include both agricultural lands receiving nitrogenous fertilizers and forests. Greater gains in DSi with respect to alkalinity losses in the Ohio-Tennessee River Basin than in the NAEW sites suggested that soils derived from younger Pleistocene glacial-till may yield more DSi relative to nitrogenous fertilizer applications than the older NAEW soils. Because silicate weathering occurs via acids released from nitrification, CO2 consumption estimates based on the assumption that silicate weathers via carbonic acid alone may be especially over-estimated in fertilized agricultural watersheds with little baseflow (i.e. 67 % overestimated in the corn till watershed). CO2 consumption estimates based on silicate weathering may be as much as 20 % lower than estimates derived from carbonic acid weathering alone for the Ohio-Tennessee River Basin between 1979–2009. Globally, this may mean that younger landscapes with soils favorable for agriculture are susceptible to fertilizer-enhanced silicate weathering. Increases in silicate weathering, however, may be offset by shifts in hydrology resulting from agricultural land management practices or even from soil silica losses in response to repeated acidification.
New estimate of chemical weathering rate in Xijiang River Basin based on multi-model
