03035nas a2200229 4500008004100000245012400041210006900165300001100234490000800245520230900253653002402562653001802586653000902604653002002613653002102633653001802654653001002672653001402682100002302696700001902719856006702738 2019 eng d00aDust, impure calcite, and phytoliths: modeled alternative sources of chemical weathering solutes in shallow groundwater0 aDust impure calcite and phytoliths modeled alternative sources o a1188710 v5273 a

In highly reactive, carbonate terrains that constitute more than one-fifth of critical zone landscapes, quantifying bedrock weathering processes may require understanding the realities of carbonate mineral impurity on solubility, biotically-produced minerals as an integral part of leaky biogeochemical cycles, and dust-deposited minerals as important high-surface-area, first-contact solute sources. The potential impact of these processes has not been thoroughly investigated as groundwater solutes are mostly thought to be sourced from chemical reactions with soil and bedrock, although dust is often viewed as an important delivery mechanism of nutrients to other ecosystems, including those in mountain and tropical settings. We present results of computer and hand-calculated (manual) inverse modeling of two years of stream-water chemistry, spanning a dry and a wet year, for a groundwater-fed headwater stream at the Konza Tallgrass Prairie Long-Term Ecological Research Site in northeastern Kansas. Weathering of the limestone and shale bedrock at the site provide a possible source of solutes to the groundwater-fed stream, but our modeling suggests an alternate source considering the pathway of groundwater recharge likely encounters highly reactive phases before encountering bedrock. We used the mineralogy and geochemistry of local dust collected previously, estimates of a possible chemical composition of phytolith containing potassium, and an impure calcite representing measured limestone bedrock chemistry to show that chemical reactions with the current dust flux are adequate to account for the groundwater chemistry. Average annual amounts were about: 1) 380 kg ha−1 yr−1 dust dissolved, 2) 80 kg ha−1 yr−1 bedrock carbonate dissolved, and 3) 320 kg ha−1 yr−1 phytoliths precipitated. Small amounts of cation exchange were also required to balance the models. There were only small differences between the computer and manual inverse models; both methods resulted in up to 4.6 times more mass of dust dissolved than bedrock. We suggest that dust weathering may be a process that occurs widely, considering the ubiquitous dust flux in continental regions.

10aChemical weathering10aCritical zone10aDust10aDust deposition10aHeadwater stream10aInverse model10aKarst10aMerokarst1 aMacpherson, G., L.1 aSullivan, P.L. uhttps://linkinghub.elsevier.com/retrieve/pii/S000925411830398X03030nas a2200229 4500008004100000245012900041210006900170300001100239490000800250520230600258653001802564653003102582653001002613653002302623100001902646700001602665700002302681700001102704700001702715700001802732856005002750 2019 eng d00aHow landscape heterogeneity governs stream water concentration-discharge behavior in carbonate terrains (Konza Prairie, USA)0 aHow landscape heterogeneity governs stream water concentrationdi a1189890 v5273 a

Mounting evidence suggests ecosystem changes that alter subsurface water fluxes and carbon dioxide concentrations in carbonate terrains may drive measurable changes in chemical weathering rates, stream water chemistry, and flow path evolution on human timescales. We test this idea by exploring if the encroachment of woody vegetation into grasslands in a carbonate terrain landscape at the Konza Prairie (KS, USA) has resulted in differences in landscape-stream connectivity and, thus, the behavior of stream water solutes. Woody encroachment (up to 60% cover) at Konza has been observed on watersheds, particularly those that experience a fire return interval of four years or greater. We focus on three headwater catchments (two grassland and one woody-encroached) and a downstream confluence, and analyze stream water discharge and chemistry (major anions, cations, and dissolved nutrients) measured from 2015 to 2016.

We observe that the woody-encroached watershed exhibits a greater area-normalized solute flux and greater degree of chemodynamic behavior for most geogenic species compared to the less encroached grassland watersheds. The downstream confluence exhibits the most chemostatic behavior for these same solutes compared to the low order watersheds. We interpret the chemodynamic behavior of the woody-encroached watersheds to arise from a greater diversity of flow paths and solute sources that contribute to this stream. End member mixing analysis (EMMA) supports this hypothesis but also indicates a possible “missing” end member which we interpret to be solutes likely derived from clay weathering along limestone-mudstone boundaries. We invoke differences in rooting systems between grass and woody species to explain the differences in flow paths and solute generation between these headwater sites given that they sit adjacent to each other, dissect the same nearly horizontal (dip 0.1–0.21°NW) lithologic units, and experience the same climate. If these processes hold true at other sites, then the globally observed encroachment of woody vegetation into grasslands may deepen flow paths and enhance chemical weathering fluxes from ecosystems, and over long-time periods alter the trajectory of soil development and landscape evolution.

10aCritical zone10aEnd member mixing analysis10aKarst10awoody encroachment1 aSullivan, P.L.1 aStops, M.W.1 aMacpherson, G., L.1 aLi, L.1 aHirmas, D.R.1 aDodds, W., K. uhttps://doi.org/10.1016/j.chemgeo.2018.12.002