Comment on “Particle fluxes in groundwater change subsurface rock chemistry over geologic time”

Over the last decade, studies at the Shale Hills Critical Zone Observatory (Shale Hills) have greatly expanded knowledge of weathering in previously understudied, shale-mantled terrains, as well as Earth's Critical Zone as a whole. Among the many discoveries made was the importance of redistribution and losses of micron-sized particles during development of shale-derived soils. A geochemical fingerprint of this process for Al and Fe was illustrated quantitatively by Jin et al. (2010). Subsequent papers, too numerous to list in a Comment, built upon this new recognition by evaluating the spatial and temporal aspects element mobilization. Recently, Kim et al. (2018) examined the composition of suspended, generally micron-sized particles in the Shale Hills stream, along with the dissolved load, across seasons and ranges of discharge.

One prominent conclusion from Kim et al. (2018) is that Zr is essentially immobile at Shale Hills. Such a broad conclusion is in direct contradiction with one from Bern and Yesavage (2018) that Zr has been mobilized from soils at Shale Hills, and the losses relative to soil parent material are significant (median 41%). The point is important, because assuming Zr immobility is necessary to index gains and losses of other elements using the open-chemical-system transport function (τ). Both papers draw upon patterns and calculations using elemental concentration data from Shale Hills and attempt to construct conceptual frameworks to explain the results. Here, the argument is made that the understanding of substantial Zr mobility from soils at Shale Hills described by Bern and Yesavage (2018) is more accurate. Additionally, issues with adaptations of the standard τ equations used in Kim et al. (2018) and some previous papers are also addressed.