skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Machine learning deciphers CO<sub>2</sub> sequestration and subsurface flowpaths from stream chemistry
Abstract. Endmember mixing analysis (EMMA) is often used by hydrogeochemiststo interpret the sources of stream solutes, but variations in streamconcentrations and discharges remain difficult to explain. We discoveredthat machine learning can be used to highlight patterns in stream chemistrythat reveal information about sources of solutes and subsurface groundwaterflowpaths. The investigation has implications, in turn, for the balance ofCO2 in the atmosphere. For example, CO2-driven weathering ofsilicate minerals removes carbon from the atmosphere over ∼106-year timescales. Weathering of another common mineral, pyrite, releases sulfuricacid that in turn causes dissolution of carbonates. In that process,however, CO2 is released instead of sequestered from the atmosphere. Thus, understanding long-term global CO2 sequestration by weatheringrequires quantification of CO2- versus H2SO4-drivenreactions. Most researchers estimate such weathering fluxes from streamchemistry, but interpreting the reactant minerals and acids dissolved in streams has been fraught with difficulty. We apply a machine-learningtechnique to EMMA in three watersheds to determine the extent of mineraldissolution by each acid, without pre-defining the endmembers. The resultsshow that the watersheds continuously or intermittently sequester CO2, but the extent of CO2 drawdown is diminished in areas heavily affectedby acid rain. Prior to applying the new algorithm, CO2 drawdown wasoverestimated. The new technique, which elucidates the importance ofdifferent subsurface flowpaths and long-timescale changes in the watersheds,should have utility as a new EMMA for investigating water resourcesworldwide.  more » « less
Award ID(s):
1331726 1639150
PAR ID:
10313541
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Hydrology and Earth System Sciences
Volume:
25
Issue:
6
ISSN:
1607-7938
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Abstract. Carbonate weathering is essential in regulating atmosphericCO2 and carbon cycle at the century timescale. Plant roots accelerateweathering by elevating soil CO2 via respiration. It however remainspoorly understood how and how much rooting characteristics (e.g., depth anddensity distribution) modify flow paths and weathering. We address thisknowledge gap using field data from and reactive transport numericalexperiments at the Konza Prairie Biological Station (Konza), Kansas (USA), asite where woody encroachment into grasslands is surmised to deepen roots. Results indicate that deepening roots can enhance weathering in two ways.First, deepening roots can control thermodynamic limits of carbonatedissolution by regulating how much CO2 transports vertical downward tothe deeper carbonate-rich zone. The base-case data and model from Konzareveal that concentrations of Ca and dissolved inorganic carbon (DIC) areregulated by soil pCO2 driven by the seasonal soil respiration. Thisrelationship can be encapsulated in equations derived in this workdescribing the dependence of Ca and DIC on temperature and soil CO2. The relationship can explain spring water Ca and DIC concentrations from multiple carbonate-dominated catchments. Second, numericalexperiments show that roots control weathering rates by regulating recharge(or vertical water fluxes) into the deeper carbonate zone and exportreaction products at dissolution equilibrium. The numerical experimentsexplored the potential effects of partitioning 40 % of infiltrated waterto depth in woodlands compared to 5 % in grasslands. Soil CO2 datasuggest relatively similar soil CO2distribution over depth, which in woodlands and grasslands leads only to 1 % to∼ 12 % difference inweathering rates if flow partitioning was kept the same between the two landcovers. In contrast, deepening roots can enhance weathering by ∼ 17 % to200 % as infiltration rates increased from 3.7 × 10−2 to 3.7 m/a. Weathering rates in these cases however are more than an order of magnitude higher than a case without roots atall, underscoring the essential role of roots in general. Numericalexperiments also indicate that weathering fronts in woodlands propagated> 2 times deeper compared to grasslands after 300 years at aninfiltration rate of 0.37 m/a. These differences in weathering fronts areultimately caused by the differences in the contact times of CO2-charged water with carbonate in the deep subsurface. Within the limitation of modeling exercises, these data and numerical experiments prompt the hypothesis that (1) deepening roots in woodlands can enhance carbonate weathering by promotingrecharge and CO2–carbonate contact in the deepsubsurface and (2) the hydrological impacts of rooting characteristics canbe more influential than those of soil CO2 distribution in modulatingweathering rates. We call for colocated characterizations of roots,subsurface structure, and soil CO2 levels, as well as their linkage to waterand water chemistry. These measurements will be essential to illuminatefeedback mechanisms of land cover changes, chemical weathering, globalcarbon cycle, and climate. 
    more » « less
  2. Abstract High latitude regions across the globe are undergoing severe modifications due to changing climate. A high latitude region of concern is the Gulf of Alaska (GoA), where these changes in hydroclimate undoubtedly affect the hydrogeochemistry of freshwater discharging to the nearshore ecosystems of the region. To fill the knowledge gap of our understanding of freshwater stream geochemistry with the GoA, we compile stream water chemistry data from 162 stream sites across the region. With an inverse model, we estimate fractional contributions to solute fluxes from weathering of silicate, carbonate, and sulfide minerals, and precipitation. We assess weathering rates across the region and compare them against global river yields. The median fractional contribution of carbonate weathering to total weathering products is 78% across all stream sites; however, there are several streams where silicate weathering is a dominant source of solutes. Weathering by sulfuric acid is elevated in glacierized watersheds. Finally, cation weathering rates are lower in GoA streams compared to the world's largest rivers; however, weathering rates are similar when compared to a global dataset of glacier fed streams. We suggest that hydrologic changes driven by glacier ice loss and increased precipitation will alter river water quality and chemical weathering regimes such that silicate weathering may become a more important source of solutes and sulfide oxidation may decrease. This contribution provides a platform to build from for future investigations into changes to stream water chemistry in the region and other high latitude watersheds. 
    more » « less
  3. Soil biota generate CO2 that can vertically export to the atmosphere, and dissolved organic and inorganic carbon (DOC and DIC) that can laterally export to streams and accelerate weathering. These processes are regulated by external hydroclimate forcing and internal structures (permeability distribution), the relative influences of which are rarely studied. Understanding these interactions is essential a hydrological extremes intensify in the future. Here we explore the question: How and to what extent do hydrological and permeability distribution conditions regulate soil carbon transformations and chemical weathering? We address the questions using a hillslope reactive transport model constrained by data from the Fitch Forest (Kansas, United States). Numerical experiments were used to mimic hydrological extremes and variable shallow-versus-deep permeability contrasts. Results demonstrate that under dry conditions (0.08 mm/day), long water transit times led to more mineralization of organic carbon (OC) into inorganic carbon (IC) form (>98\%). Of the IC produced, ~ 75\% was emitted upward as CO2 gas and ~ 25\% was exported laterally as DIC into the stream. Wet conditions (8.0 mm/day) resulted in less mineralization (~88\%), more DOC production (~12\%), and more lateral fluxes of IC (~50\% of produced IC). Carbonate precipitated under dry conditions and dissolved under wet conditions as the fast flow rapidly droves the reaction to disequilibrium. The results depict a conceptual hillslope model that prompts four hypotheses for our community to test. H1: Droughts enhance carbon mineralization and vertical upward carbon fluxes, whereas large hydrological events such as storms and flooding enhance subsurface vertical connectivity, reduce transit times, and promote lateral export. H2: The role of weathering as a net carbon sink or source to the atmosphere depends on the interaction between hydrologic flows and lithology: transition from droughts to storms can shift carbonate from a carbon sink (mineral precipitation) to carbon source (dissolution). H3: Permeability contrasts regulate the lateral flow partitioning via shallow flow paths versus deeper groundwater though this alter reaction rates negligibly. H4: Stream chemistry reflect flow paths and can potentially quantify water transit times: solutes enriched in shallow soils have a younger water signature; solutes abundant at depth carry older water signature. 
    more » « less
  4. null (Ed.)
    Abstract. During the early part of the last glacial termination (17.2–15 ka) and coincident with a ∼35 ppm rise in atmospheric CO2, a sharp 0.3‰–0.4‰ decline in atmospheric δ13CO2 occurred, potentially constraining the key processes that account for the early deglacial CO2 rise. A comparable δ13C decline has also been documented in numerous marine proxy records from surface and thermocline-dwelling planktic foraminifera. The δ13C decline recorded in planktic foraminifera has previously been attributed to the release of respired carbon from the deep ocean that was subsequently transported within the upper ocean to sites where the signal was recorded (and then ultimately transferred to the atmosphere). Benthic δ13C records from the global upper ocean, including a new record presented here from the tropical Pacific, also document this distinct early deglacial δ13C decline. Here we present modeling evidence to show that rather than respired carbon from the deep ocean propagating directly to the upper ocean prior to reaching the atmosphere, the carbon would have first upwelled to the surface in the Southern Ocean where it would have entered the atmosphere. In this way the transmission of isotopically light carbon to the global upper ocean was analogous to the ongoing ocean invasion of fossil fuel CO2. The model results suggest that thermocline waters throughout the ocean and 500–2000 m water depths were affected by this atmospheric bridge during the early deglaciation. 
    more » « less
  5. Abstract Volcanic arcs are chemical weathering hotspots that may contribute disproportionately to global CO2consumption through silicate weathering. Accurately modeling the impact of volcanic‐arc landscapes on the Earth's long‐term carbon cycle requires understanding how climate and physical erosion control weathering fluxes from arc landscapes. We evaluate these controls by examining the covariation of stream solutes, sediment geochemistry, and long‐term physical erosion fluxes inferred from cosmogenic36Cl in magnetite in volcanic watersheds in Puerto Rico that span a ca. 15‐fold gradient in specific discharge. Analysis of this data using power‐law relationships demonstrates that CO2consumption from arc‐rock weathering in the humid tropics is more strongly limited by physical erosion and the supply of primary minerals to the weathering zone than by temperature or the flux of fresh, chemically reactive waters through the critical zone. However, a positive correlation between long‐term physical erosion fluxes and specific discharge is also observed. This indicates that fresh mineral supply in arc environments may ultimately depend on precipitation rates, which may maintain a coupling between arc‐rock weathering fluxes and climate under principally supply limited weathering conditions. 
    more » « less