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1. Paleothermometry of an enigmatic travertine deposit: Cottonwood Travertine, Stillwater Range, NV

   Jackson, A. ( February 2023 , Proceedings 48th Workshop on Geothermal Reservoir Engineering, Stanford University, Stanford, California.)

   ABSTRACT Hot and cold spring travertine deposits record integrated histories reflecting changing hydrologic conditions, informing our understanding of the driving forces behind factors impacting local hydrology. We present results from a geologic and geochemical investigation of Cottonwood Travertine, located in Dixie Valley, NV, where it is unclear if the paleospring system that deposited the travertine was driven by deeply sourced hydrothermal fluids, or high fluid flow driven by wetter paleoclimate conditions. The temperature of the spring water that precipitated the Cottonwood Travertine has implications for the relative importance of hydrothermal versus climatic processes influencing the formation and cessation of this enigmatic deposit. We identified four groups of samples based on geologic setting, sample textures, and stable and clumped isotopic analysis: 1) calcite cemented upper gravels, 2) a mound area at the upper bench of the deposit, 3) samples from the flanks and from vuggy veins and fault zone cements from the base of the deposit, and 4) fibrous sub-travertine veins. The calcite-cemented gravels yielded δ18OC values as low as -18.4‰ (VPDB) and apparent TΔ47 of 52°C. The top mound of the deposit returned calcite δ18OC values between -12.8‰ and -11.7‰ (VPDB) and clumped isotope temperatures (TD47) of 24 – 32°C. Higher d13C and d18Oc values at the mound site are interpreted to reflect off gassing of CO2 and disequilibrium conditions. δ18OC and TD47 values from the slopes and base of the deposit are between -15.9‰ and -14.5‰ (VPDB) and around 20°C, respectively. Structurally, texturally, and isotopically (δ18OC = -29.4‰ (VPDB); TΔ47 = 93°C), the fibrous sub-travertine veins are more consistent with the local Jurassic host rock and probably do not reflect recent hot spring conditions. Our analysis suggests that, despite the impressive volume, Cottonwood Travertine formed from springs that were not particularly hot, and the deposit instead reflects vigorous warm spring activity in a wetter climactic regime rather than fluid flow from an extinct higher temperature hydrothermal system. 

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2. Oceanic cooling recorded in shells spanning the Medieval Climate Anomaly in the subtropical eastern North Atlantic Ocean

   Parker, W.G. ( January 2020 , Quaternary science reviews)

   The Medieval Climate Anomaly (MCA; 900e1300 AD) was the most recent period of pre-industrial climatic warming in the northern hemisphere, and thus estimations of MCA signals can illuminate possible impacts of anthropogenic climate change. Current high-resolution MCA climate signals are restricted to mid- and high-latitude regions, which confounds inferences of how the MCA impacted some global/hemispheric climate mechanisms (e.g. North Atlantic Oscillation; NAO). To address this knowledge gap, we estimate seasonally-resolved sea surface temperatures (SSTs) from the oxygen isotope composition (d18O) of serially sampled Phorcus atratus shells from archaeological sites spanning the MCA in the Canary Islands. Twelve archaeological and six modern P. atratus shells were analyzed, and archaeological shells were dated using carbonate-target radiocarbon dating. SSTs were estimated using the published aragonite-water equilibrium fractionation equation. Modern shells showed a mean SST of 20.0 ± 1.5
   C, with a seasonal amplitude of 5.3 ± 0.9
   C. Archaeological shells exhibited a mean SST of 18.2 ± 0.7
   C, with a mean seasonal amplitude of 5.5 ± 1.0
   C. Thus, shells that span the MCA in the Canary Islands recorded SSTs that were significantly cooler than the modern (P < .05), contrasting with warming estimates and model predictions elsewhere in the Northern Hemisphere. We propose that the observed cooling resulted from increased upwelling in NW Africa due to a strengthening of the prevailing westerlies and coastal winds along the African shoreline. The intensified upwelling scenario during the MCA is partially supported by in-situ carbon isotope data (d13C) retrieved from the archaeological shells, which was compared to the d13C values of modern shells and dissolved inorganic carbon in the ambient seawater. These results are consistent with other low-latitude temperature/precipitation anomalies associated with a positive NAO mode, suggesting a transition to a positive NAO index during the middle and late MCA that possibly extended later into the 13th century AD. 

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3. Enhancing understanding of the hydrological cycle via pairing of process‐oriented and isotope ratio tracers

   https://doi.org/10.5061/dryad.8w9ghx3mr  

   Fiorella, Richard ; Siler, Nicholas ; Nusbaumer, Jesse ; Noone, David ( January 2021 , Dryad)

   This dataset contains monthly average output files from the iCAM6 simulations used in the manuscript "Enhancing understanding of the hydrological cycle via pairing of process-oriented and isotope ratio tracers," in review at the Journal of Advances in Modeling Earth Systems. A file corresponding to each of the tagged and isotopic variables used in this manuscript is included. Files are at 0.9° latitude x 1.25° longitude, and are in NetCDF format. Data from two simulations are included: 1) a simulation where the atmospheric model was "nudged" to ERA5 wind and surface pressure fields, by adding an additional tendency (see section 3.1 of associated manuscript), and 2) a simulation where the atmospheric state was allowed to freely evolve, using only boundary conditions imposed at the surface and top of atmosphere. Specific information about each of the variables provided is located in the "usage notes" section below. Associated article abstract: The hydrologic cycle couples the Earth's energy and carbon budgets through evaporation, moisture transport, and precipitation. Despite a wealth of observations and models, fundamental limitations remain in our capacity to deduce even the most basic properties of the hydrological cycle, including the spatial pattern of the residence time (RT) of water in the atmosphere and the mean distance traveled from evaporation sources to precipitation sinks. Meanwhile, geochemical tracers such as stable water isotope ratios provide a tool to probe hydrological processes, yet their interpretation remains equivocal despite several decades of use. As a result, there is a need for new mechanistic tools that link variations in water isotope ratios to underlying hydrological processes. Here we present a new suite of “process-oriented tags,” which we use to explicitly trace hydrological processes within the isotopically enabled Community Atmosphere Model, version 6 (iCAM6). Using these tags, we test the hypotheses that precipitation isotope ratios respond to parcel rainout, variations in atmospheric RT, and preserve information regarding meteorological conditions during evaporation. We present results for a historical simulation from 1980 to 2004, forced with winds from the ERA5 reanalysis. We find strong evidence that precipitation isotope ratios record information about atmospheric rainout and meteorological conditions during evaporation, but little evidence that precipitation isotope ratios vary with water vapor RT. These new tracer methods will enable more robust linkages between observations of isotope ratios in the modern hydrologic cycle or proxies of past terrestrial environments and the environmental processes underlying these observations.   Details about the simulation setup can be found in section 3 of the associated open-source manuscript, "Enhancing understanding of the hydrological cycle via pairing of process‐oriented and isotope ratio tracers." In brief, we conducted two simulations of the atmosphere from 1980-2004 using the isotope-enabled version of the Community Atmosphere Model 6 (iCAM6) at 0.9x1.25° horizontal resolution, and with 30 vertical hybrid layers spanning from the surface to ~3 hPa. In the first simulation, wind and surface pressure fields were "nudged" toward the ERA5 reanalysis dataset by adding a nudging tendency, preventing the model from diverging from observed/reanalysis wind fields. In the second simulation, no additional nudging tendency was included, and the model was allowed to evolve 'freely' with only boundary conditions provided at the top (e.g., incoming solar radiation) and bottom (e.g., observed sea surface temperatures) of the model. In addition to the isotopic variables, our simulation included a suite of 'process-oriented tracers,' which we describe in section 2 of the manuscript. These variables are meant to track a property of water associated with evaporation, condensation, or atmospheric transport. Metadata are provided about each of the files below; moreover, since the attached files are NetCDF data - this information is also provided with the data files. NetCDF metadata can be accessed using standard tools (e.g., ncdump). Each file has 4 variables: the tagged quantity, and the associated coordinate variables (time, latitude, longitude). The latter three are identical across all files, only the tagged quantity changes. Twelve files are provided for the nudged simulation, and an additional three are provided for the free simulations: Nudged simulation files iCAM6_nudged_1980-2004_mon_RHevap: Mass-weighted mean evaporation source property: RH (%) with respect to surface temperature. iCAM6_nudged_1980-2004_mon_Tevap: Mass-weighted mean evaporation source property: surface temperature in Kelvin iCAM6_nudged_1980-2004_mon_Tcond: Mass-weighted mean condensation property: temperature (K) iCAM6_nudged_1980-2004_mon_columnQ: Total (vertically integrated) precipitable water (kg/m2).  Not a tagged quantity, but necessary to calculate depletion times in section 4.3 (e.g., Fig. 11 and 12). iCAM6_nudged_1980-2004_mon_d18O: Precipitation d18O (‰ VSMOW) iCAM6_nudged_1980-2004_mon_d18Oevap_0: Mass-weighted mean evaporation source property - d18O of the evaporative flux (e.g., the 'initial' isotope ratio prior to condensation), (‰ VSMOW) iCAM6_nudged_1980-2004_mon_dxs: Precipitation deuterium excess (‰ VSMOW) - note that precipitation d2H can be calculated from this file and the precipitation d18O as d2H = d-excess - 8*d18O. iCAM6_nudged_1980-2004_mon_dexevap_0: Mass-weighted mean evaporation source property - deuterium excess of the evaporative flux iCAM6_nudged_1980-2004_mon_lnf: Integrated property - ln(f) calculated from the constant-fractionation d18O tracer (see section 3.2). iCAM6_nudged_1980-2004_mon_precip: Total precipitation rate in m/s. Note there is an error in the metadata in this file - it is total precipitation, not just convective precipitation. iCAM6_nudged_1980-2004_mon_residencetime: Mean atmospheric water residence time (in days). iCAM6_nudged_1980-2004_mon_transportdistance: Mean atmospheric water transport distance (in km). Free simulation files iCAM6_free_1980-2004_mon_d18O: Precipitation d18O (‰ VSMOW) iCAM6_free_1980-2004_mon_dxs: Precipitation deuterium excess (‰ VSMOW) - note that precipitation d2H can be calculated from this file and the precipitation d18O as d2H = d-excess - 8*d18O. iCAM6_free_1980-2004_mon_precip: Total precipitation rate in m/s. Note there is an error in the metadata in this file - it is total precipitation, not just convective precipitation. 

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4. Coprecipitation of Crystalline Calcium Silicates and Carbonates from the Hydrothermal Reaction of Pseudowollastonite

   https://doi.org/10.1021/acssuschemeng.3c05110  

   Tolliver, Coleman ; Nguyen, Suzanne ; Dela Cerna, Kimmie ; McNamara, Rachel ; Opila, Elizabeth J. ; Clarens, Andres F. ( February 2024 , ACS Sustainable Chemistry & Engineering)

   Calcium silicates are abundant, but sparingly soluble, feedstocks of interest for making low-carbon alternative cements. Under hydrothermal and alkaline conditions, they can form crystalline calcium silicate hydrate (CCSH) products, which are abundant in Roman concrete, or they can form carbonates when CO2 is present. To understand when co-precipitation of CCSH and carbonate phases is possible, we studied the hydrothermal carbonation of a model calcium silicate, pseudowollastonite (-CaSiO3), at 150ºC and high pH as a function of CO2 source (CO2(g) or Na2CO3) and different concentrations of sodium, alumina, and silica. Our experiments produced a range of CCSH phases including tobermorite – 13Å, rhodesite, and pectolite, as early as one day after the start of our experiments. About 10.7% hydrated product was observed after 7 days of curing in 2 M NaOH solution. We also observed the formation of CaCO3 as both aragonite and calcite when carbon was introduced to our experimental system. The carbon source impacted the ratio of CaCO3 to CCSH phases in the reaction products. Availability of Na2CO3 produced a balance between CaCO3 and CCSH phases whereas CO2(g) produced more CaCO3 at about 36.4% by mass at the highest. Higher concentrations of Na+ increased precipitation of both CaCO3 and/or CCSH phases. The presence of excess silica, in the form of dissolved borosilicate glass from our reaction vessels under alkaline reaction conditions, also enhanced the formation of CCSH phases formed in some experiments. Supplemental Al2O3, a common constituent in many silicate feedstocks, also enhanced CCSH formation, likely by forming aluminum substituted phases under the conditions tested here. These chemical insights can be enabling in designing formulation and curing guidelines for novel cementitious materials. 

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5. Triple oxygen isotopes in evolving continental crust, granites, and clastic sediments

   Bindeman, Ilya N ( October 2020 , Reviews in mineralogy and geochemistry)

   This Chapter considers triple oxygen isotope variations and their 4 Gyr temporal evolution in bulk siliciclastic sedimentary rocks and in granites. The d18O and D'17O values provide new insights into weathering in the modern and ancient hydrosphere and coeval crustal petrogenesis. We make use of the known geological events and processes that affect the rock cycle: supercontinent assembly and breakup that influence continent-scale and global climate, the fraction of the exposed crust undergoing weathering, and isotopic values of precipitation. New data from a 5000 m Texas drillhole into the Oligocene Frio Formation demonstrate minimal isotopic shifts from mudrocks to shales during diagenesis, mostly related to expulsion of water from smectite-rich loosely cemented sediment and its conversion to illite-rich shale. Inversion of triple oxygen isotope fractionations return isotopic values and temperatures along the hole depth that are more consistent with weathering conditions in the Oligocene and modern North America (d18O = -7 to -15‰, and T of +15 to +45°C) rather than d18O from 8 to 10‰ diagenetic water in the drill hole at 175-195°C. More precise T and d18Owater are obtained where the chemical index of alteration (CIA) based detrital contribution is subtracted from these sediments. Triple oxygen isotopes from suspended sediments in major world rivers record conditions (T and d18Ow) of their watersheds, and not the composition of bedrock because weathering is water-dominated. In parallel, the Chapter presents new analyses of 100 granites, orthogneisses, migmatites, tonalite-trondhjemite-granodiorite (TTG), and large-volume ignimbrites from around the world that range in age from 4 Ga to modern. Most studied granites are orogenic and anatectic in origin and represent large volume remelting/assimilation of shales and other metasediments; the most crustal and high-d18O of these are thus reflect and record the average composition of evolving continental crust. Granites also develop a significant progressive increase in d18O values from 6-7‰ (4-2.5 Ga) to 10-13‰ (~1.8-1.2 Ga) after which d18O stays constant or even decreases. More importantly, we observe a moderate -0.03‰ step-wise decrease in D'17O between 2.1 and 2.5 Ga, which is about half of the step-wise decrease observed in shales over this time interval. We suggest that granites, as well as shales, record the significant advent and greater volumetric appearance of low-D'17O, high-d18O weathering products (shales) altered by meteoric waters upon rapid emergence of large land masses at ~2.4 Ga, although consider alternative interpretations. These weathering products were incorporated into abundant 2.0-1.8 Ga orogens around the world, where upon remelting, they passed their isotopic signature to the granites. We further observe the dichotomy of high-D'17O Archean shales, and unusually low-D'17O Archean granites. We attribute this to greater contribution from shallow crustal hydrothermal contribution to shales in greenstone belts, while granites in the earliest 3.0-4.0 Ga crust and TTGs require involvement of hydrothermal products with lower-D'17O signatures at moderately high-d18O, which we attribute to secondary silicification of their protoliths before partial melting. The Chapter further discusses evolution of the shale record through geologic history and discusses the step-wise change in d18O and D'17O values at Archean/Proterozoic transition. Denser coverage for shales in the past 1 billion years permits investigation of the rocks and their weathering in the last supercontinent cycle, with observed lighter d18O values, characteristic for the mid-Phanerozoic at the initiation of Gondwana breakup. The continuing increase in d18O values of the shales since 4 Ga is interpreted to reflect accumulation of weathering products via shale accretion to continents, as low-density and buoyant shales tend to not subduct back into the mantle. The rock cycle passes triple oxygen isotopic signatures from precipitation to sedimentary, metasedimentary, and finally to anatectic igneous rocks. Continental crust became progressively heavier in d18O, lighter in D'17O due to incremental accumulation of high-d18O sediments in accretionary wedges. Second-order trends in d18O and D'17O are due to supercontinent cycles and glacial episodes. 

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