skip to main content


Title: Concentration-runoff relationships of contrasting small mountainous rivers in the Pacific Northwest, USA: Insights into the weathering of rhenium relative to other weathering products
This study examines dissolved rhenium (Re) concentrations as a function of water runoff using river samples from two contrasting mountainous watersheds, the Eel and Umpqua Rivers in the Pacific Northwest, USA. These watersheds share many key characteristics in terms of size, discharge, climate, and vegetation, but they have a 15-fold difference in sediment yield due to differences in their tectonic setting and uplift and erosion rates. We evaluate concentration-runoff (C-R) relationships and ratios of coefficients of variation (CVC/CVR) for major cations, anions, dissolved inorganic carbon, selected trace elements including Re, and 87Sr/86Sr ratios. Recent research outlines the potential of Re to serve as a tracer for the oxidation of ancient/fossil organic matter because of its close association with petrogenic carbon (OCpetro) in rocks. In both the Eel and Umpqua Rivers, our measurements show that Re behaves similarly to major weathering derived-solutes corrected for atmospheric input, such as Ca2+*, Mg2+*, and Na+* with modest dilution across all tributaries with increasing runoff. Rhenium behaves dissimilarly from other trace elements, such as Mo and U, and is also dissimilar to biologically-cycled nutrients, such as NO3 – , PO4 3 , and K+*, suggesting differences in sources, solute generation mechanisms, and flowpaths. Rhenium behavior is also distinct from that of colloids, which have increasing concentrations with increasing runoff. We find that Re and sulfate corrected for atmospheric input (SO4 2 *) have distinct CR relationships, in which SO4 2 * undergoes greater dilution with increasing runoff. This implies that Re is not dominantly sourced from sulfide weathering, which leaves primary bedrock minerals and OCpetro hosted in bedrock of these watersheds as the likely dominant sources of dissolved Re release. At mean discharge, Re concentration in the Eel river (3.5 pmol L-1) is more than two times greater than Re concentrations in the Umpqua River (1.5 pmol L-1). Furthermore, comparison of two tributary watersheds with similar bedrock but marked differences in erosion rates show higher Re concentrations in Bull Creek (erosion rate of 0.5 mm yr 1) relative to Elder Creek (erosion rate of 0.2 mm yr 1). The results of this study suggest that dissolved Re in the Eel and Umpqua River basins is likely derived from primary mineral dissolution or OCpetro oxidation, and Re fluxes are higher in areas with higher erosion rates, suggesting that tectonic setting is one factor that controls Re release and therefore OCpetro oxidation.  more » « less
Award ID(s):
1655506
NSF-PAR ID:
10479856
Author(s) / Creator(s):
; ; ; ;
Publisher / Repository:
Geochimica et Cosmochimica Acta
Date Published:
Journal Name:
Geochimica et Cosmochimica Acta
Volume:
337
Issue:
C
ISSN:
0016-7037
Page Range / eLocation ID:
106 to 122
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Lithium isotope ratios (δ7Li) of rivers are increasingly serving as a diagnostic of the balance between chemical and physical weathering contributions to overall landscape denudation rates. Here, we show that intermediate weathering intensities and highly enriched stream δ7Li values typically associated with lowland floodplains can also describe small upland watersheds subject to cool, wet climates. This behavior is revealed by stream δ7Li between +22.4 and +23.5‰ within a Critical Zone observatory located in the Cévennes region of southern France, where dilute stream solute concentrations and significant atmospheric deposition otherwise mask evidence of incongruence. The water‐rock reaction pathways underlying this behavior are quantified through a multicomponent, isotope‐enabled reactive transport model. Using geochemical characterization of soil profiles, bedrock, and long‐term stream samples as constraints, we evolve the simulation from an initially unweathered granite to a steady state weathering profile which reflects the balance between (a) fluid infiltration and drainage and (b) bedrock uplift and soil erosion. Enriched stream δ7Li occurs because Li is strongly incorporated into actively precipitating secondary clay phases beyond what prior laboratory experiments have suggested. Chemical weathering incongruence is maintained despite relatively slow reaction rates and moderate clay accumulation due to a combination of two factors. First, reactive primary mineral phases persist across the weathering profile and effectively “shield” the secondary clays from resolubilization due to their greater solubility. Second, the clays accumulating in the near‐surface profile are relatively mature weathering byproducts. These factors promote characteristically low total dissolved solute export from the catchment despite significant input of exogenous dust.

     
    more » « less
  2. Abstract

    There is a critical knowledge gap about how glacier retreat in remote and rapidly warming tropical montane watersheds will impact solute export, which has implications for downstream geochemical cycling and ecological function. Because tropical glacierized watersheds are often uniquely characterized by year‐round ablation, upslope vegetation migration, and significant groundwater flow, baseline understanding is needed of how spatiotemporal variables within these watersheds control outlet hydrochemistry. We implemented a recently developed reactive transport watershed model, BioRT‐Flux‐PIHM, for a sub‐humid glacierized watershed in the Ecuadorian Andes with young volcanic soils and fractured bedrock. We found a unique simulated concentration and discharge (C‐Q) pattern that was mostly chemostatic but superimposed by dilution episodes. The chemostatic background was attributed to large simulated contributions of groundwater (subsurface lateral flow) to streamflow, of which a notable fraction (37%) comprised infiltrated ice‐melt. Relatively constant concentrations were further maintained in the model because times and locations of lower mineral surface wetting and dissolution were offset by concentrating effects of greater evapotranspiration. Ice‐melt did not all infiltrate in simulations, especially during large precipitation events, when high surface runoff contributions to discharge triggered dilution episodes. In a model scenario without ice‐melt, major ion concentrations, including Na+, Ca2+, and Mg2+, became more strongly chemostatic and higher, but weathering rates decreased, attenuating export by 23%. We expect this reduction to be exacerbated by higher evapotranspiration and drier conditions with expanded vegetation. This work brings to light the importance of subsurface meltwater flow, ecohydrological variability, and interactions between melt and precipitation for controlling hydrochemical processes in tropical watersheds with rapidly retreating glaciers.

     
    more » « less
  3. Abstract

    Sediment grain size links sediment production, weathering, and fining from fractured bedrock on hillslopes to river incision and landscape relief. Yet models of sediment grain size delivery to rivers remain unconstrained due to a scarcity of field data. We analyzed how bedrock fracture spacing and hillslope weathering influence landscape‐scale patterns in surface sediment grain size across gradients of erosion rate and hillslope bedrock exposure in the San Gabriel Mountains (SGM) and northern San Jacinto Mountains (NSJM) of California, USA. Using ground‐based structure‐from‐motion photogrammetry models of 50 bedrock cliffs, we showed that fracture density is ~5 times higher in the SGM than the NSJM. 274 point‐count‐surveys of surface sediment grain size measured in the field and from imagery show a drainage area control on sediment grain size, with systematic downslope coarsening on hillslopes and in headwater‐colluvial channels transitioning to downstream fining in fluvial channels. In contrast to prior work and predictions from a hillslope weathering model, grain size does not increase smoothly with increasing erosion rate. For soil‐mantled landscapes, sediment grain size increases with increasing erosion rates; however, once bare bedrock emerges on hillslopes, sediment grain size in both the NSJM and SGM becomes insensitive to further increases in erosion rate and hillslope bedrock exposure, and instead reflects fracture spacing contrasts between the NSJM and SGM. We interpret this threshold behavior to emerge in steep landscapes due to efficient delivery of coarse sediment from bedrock hillslopes to channels and the relative immobility of coarse sediment in fluvial channels.

     
    more » « less
  4. The rate of chemical weathering has been observed to increase with the rate of physical erosion in published comparisons of many catchments, but the mechanisms that couple these processes are not well understood. We investigated this question by exam- ining the chemical weathering and porosity profiles from catchments developed on marine shale located in Pennsylvania, USA (Susquehanna Shale Hills Critical Zone Observatory, SSHCZO); California, USA (Eel River Critical Zone Observatory, ERC- ZO); and Taiwan (Fushan Experimental Forest). The protolith compositions, protolith porosities, and the depths of regolith at these sites are roughly similar while the catchments are characterized by large differences in erosion rate (1–3 mm yr􏱝1 in Fushan 􏱞 0.2–0.4 mm yr􏱝1 in ERCZO 􏱞 0.01–0.025 mm yr􏱝1 in SSHCZO). The natural experiment did not totally isolate erosion as a variable: mean annual precipitation varied along the erosion gradient (4.2 m yr􏱝1 in Fushan > 1.9 m yr􏱝1 in ERCZO > 1.1 m yr􏱝1 in SSHCZO), so the fastest eroding site experiences nearly twice the mean annual temperature of the other two. Even though erosion rates varied by about 100􏱟, the depth of pyrite and carbonate depletion (defined here as regolith thickness) is roughly the same, consistent with chemical weathering of those minerals keeping up with erosion at the three sites. These minerals were always observed to be the deepest to react, and they reacted until 100% depletion. In two of three of the catchments where borehole observations were available for ridges, these minerals weathered across narrow reaction fronts. On the other hand, for the rock-forming clay mineral chlorite, the depth interval of weathering was wide and the extent of depletion observed at the land surface decreased with increasing erosion/precipitation. Thus, chemical weathering of the clay did not keep pace with erosion rate. But perhaps the biggest difference among the shales is that in the fast-eroding sites, microfractures account for 30–60% of the total porosity while in the slow-eroding shale, dissolution could be directly related to secondary porosity. We argue that the microfractures increase the influx of oxygen at depth and decrease the size of diffusion-limited internal domains of matrix, accelerating weathering of pyrite and carbonate under high erosion-rate condi- tions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales. 
    more » « less
  5. Silicate weathering and organic carbon (OC) burial in soil regulate atmospheric CO2, but their influence on each other remains unclear. Generally, OC oxidation can generate acids that drive silicate weathering, yet clay minerals that form during weathering can protect OC and limit oxidation. This poses a conundrum where clay formation and OC preservation either compete or cooperate. Debate remains about their relative contributions because quantitative tools to simultaneously probe these processes are lacking while those that exist are often not measured in concert. Here we demonstrate that Li isotope ratios of sediment, commonly used to trace clay formation, can help constrain OC cycling. Measurements of river suspended sediment from two watersheds of varying physiography and analysis of published data from Hawaii soil profiles show negative correlations between solid-phase d7Li values and OC content, indicating the association of clay mineral formation with OC accumulation. Yet, the localities differ in their ranges of d7Li values and OC contents, which we interpret with a model of soil formation. We find that temporal trends of Li isotopes and OC are most sensitive to mineral dissolution/clay formation rates, where higher rates yield greater OC stocks and lower d7Li values. Whereas OC-enhanced dissolution primarily dictates turnover times of OC and silicate minerals, clay protection distinctly modifies soil formation pathways and is likely required to explain the range of observations. These findings underscore clay mineral formation, driven primarily by bedrock chemistry and secondarily by climate, as a principal modulator of weathering fluxes and OC accumulation in soil. 
    more » « less