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1. Spatiotemporal Drivers of Hydrochemical Variability in a Tropical Glacierized Watershed in the Andes

   https://doi.org/10.1029/2020WR028722  

   Saberi, Leila; Crystal Ng, G. ‐H.; Nelson, Leah; Zhi, Wei; Li, Li; La Frenierre, Jeff; Johnstone, Morgan (May 2021, Water Resources Research)

   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. 

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2. Chemical Weathering and Physical Erosion Fluxes From Serpentinite in Puerto Rico

   https://doi.org/10.1029/2024JF007776  

   Moore, Angus K; Méndez_Méndez, Kimberly; Hughes, K Stephen; Granger, Darryl E (January 2025, Journal of Geophysical Research: Earth Surface)

   Abstract Weathering of ultramafic rocks emplaced at low latitude during arc‐arc and arc‐continent collisions may provide an important sink for atmospheric CO₂over geologic timescales. Accurately modeling the effects of ultramafic rock weathering on Earth's carbon cycle and climate requires understanding mass fluxes from ultramafic landscapes. In this study, physical erosion and chemical weathering fluxes and weathering intensity are quantified in 15 watersheds across the Monte del Estado, a serpentinite massif in Puerto Rico, using measurements of in situ³⁶Cl in magnetite, stream solute fluxes, and sediment geochemistry. Despite high relief in the study watersheds, erosion fluxes are moderate (22–109 tons km⁻² yr⁻¹), chemical weathering fluxes are large (55–143 tons km⁻² yr⁻¹), and weathering intensities are among the highest yet reported for silicate‐rock weathering (up to 0.88). We use these data to parameterize power‐law relationships between weathering, erosion, and runoff. We interpret the relative importance of climate versus erosion in setting weathering fluxes and CO₂consumption from the best‐fit power‐law slopes. Weathering fluxes from tropical, montane serpentinite landscapes are found to be strongly controlled by runoff and weakly controlled by the supply of fresh rock to the weathering zone through physical erosion. The strong runoff dependence of weathering fluxes implies that, to the extent that precipitation rates are coupled to global temperature, ultramafic landscapes may be important participants in the negative silicate weathering feedback, increasing (decreasing) CO₂consumption in response to a warming (cooling) climate. Thus, serpentinite landscapes may help stabilize Earth's climate state through time. 

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3. Concentration-runoff relationships of contrasting small mountainous rivers in the Pacific Northwest, USA: Insights into the weathering of rhenium relative to other weathering products

   https://doi.org/10.1016/j.gca.2022.09.036  

   Ghazi, Layla; Goñi, Miguel; Haley, Brian A.; Muratli, Jesse M.; Pett-Ridge, Julie C. (November 2022, Geochimica et Cosmochimica Acta)

   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. 

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4. The Hydrochemical Signature of Incongruent Weathering in Iceland

   https://doi.org/10.1029/2021JF006450  

   Cole, Trevor L.; Torres, Mark A.; Kemeny, Preston C. (June 2022, Journal of Geophysical Research: Earth Surface)

   Abstract Basaltic watersheds such as those found in Iceland are thought to be important sites of CO₂sequestration via silicate weathering. However, determining the magnitude of CO₂uptake depends on accurately interpreting river chemistry. Here, we compile geochemical data from Iceland and use them to constrain weathering processes. Specifically, we use a newly developed inverse model to quantify solute supply from rain and hydrothermal fluids as well as allow for variable silicate end‐member compositions, solutes to be removed via secondary phase formation, and some Ca to be sourced from carbonate dissolution. While some of these processes have been considered previously, they have not been considered together allowing us to newly determine their relative contributions. We find that weathering in Iceland is incongruent in two ways. First, solute release from primary silicates is characterized by a higher proportion of Na than would be expected from bulk basalts, which may reflect preferential weathering or some contribution from rhyolites. This Na enrichment is further enhanced by preferential Mg and K uptake by secondary phases. No samples in our data set (n = 537) require carbonate dissolution even if isotopic data (δ²⁶Mg,δ³⁰Si,δ⁴⁴Ca, and/or⁸⁷Sr/⁸⁶Sr) are included. While some carbonate weathering is allowable, silicate weathering likely dominates. The complexity we observe in Iceland underscores the need for inverse models to account for a wide range of processes and end‐members. Given that riverine fluxes from Iceland are more Na‐rich than expected for congruent basalt weathering, the characteristic timescale of CO₂drawdown is likely affected. 

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5. Isotope Ratio – Discharge Relationships of Solutes Derived From Weathering Reactions

   https://doi.org/10.2475/001c.84469  

   Druhan, Jennifer L.; Benettin, Paolo (January 2023, American Journal of Science)

   To date, the vast majority of studies seeking to link discharge to solute concentrations have been based on representations of fluid age distributions in watersheds that are time-invariant. As increasingly detailed spatial and temporal datasets become available for weathering-derived riverine solute concentrations, the capacity to link this mass flux to transient routing of reactive fluids through Critical Zone environments is vital to quantitative interpretation. Relationships between fluid age distributions and the stable isotope ratios of these geogenic solutes are even less developed, yet these signatures are vital to parsing the suite of water-rock-life interactions that create concentration-discharge relationships. Here we offer the first merging of a hydrological model featuring time-variant fluid age distributions with a geochemical model for isotopically fractionating weathering reactions. Using SiO_2(aq)and the corresponding silicon isotope ratio $\delta$³⁰Si as an example, we show that the stable isotope signatures of riverine solutes produced by weathering reactions reflect a component of the fluid age distribution that is unique to the corresponding solute concentrations. This distinct sensitivity is the result of a stronger link between isotope ratios and the age distribution parameters describing a given watershed. This novel modeling framework is used to provide a quantitative basis for the interpretation of SiO_2(aq)and $\delta$³⁰Si in six low-order streams spread across a diversity of climates, geologies, and ecosystems. To our knowledge, this is the first forward and process-based model to describe the isotopic signatures of solutes derived from weathering reactions in watersheds subject to time-varying discharge. 

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