DOCSLIB.ORG

Quantifying Isotopic Signatures of N<Sub>2</Sub>O Using Quantum Cascade Laser Absorption Spectroscopy

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Quantifying Isotopic Signatures of N<Sub>2</Sub>O Using Quantum Cascade Laser Absorption Spectroscopy 232 CHIMIA 2019, 73, No. 4 Laureates: Junior Prizes of the sCs faLL Meeting 2018 doi:10.2533/chimia.2019.232 Chimia 73 (2019) 232–238 © Swiss Chemical Society Quantifying Isotopic Signatures of N O Using Quantum Cascade Laser 2 Absorption Spectroscopy Kristýna Kantnerováa§, Béla Tuzsona, Lukas Emmeneggera, Stefano M. Bernasconib and Joachim Mohna* §SCS-Metrohm Award for best oral presentation in Analytical Sciences Abstract: Nitrous oxide, N O, is the environmentally most relevant constituent of the biogeochemical nitrogen 2 cycle. Human activities, e.g. the agricultural use of mineral fertilizers, accelerate nitrogen transformations, leading to higher emissions of this strong greenhouse gas. Investigating the stable isotopic composition of N O provides 2 a better understanding of formation mechanisms to disentangle its variable source and sink processes. Mid- infrared (mid-IR) laser spectroscopy is a highly attractive technique to analyze N O isotopocules based on their 2 specific ro-vibrational absorption characteristics. Specifically, quantum cascade laser absorption spectroscopy (QCLAS) in combination with preconcentration has shown to be powerful for simultaneous and high-precision analysis of the main N O isotopocules. Recently, in the scope of my PhD project, we have been advancing this 2 analytical technique for the analysis of the very rare doubly substituted N O isotopic species 15N14N18O, 14N15N18O, 2 and 15N15N16O, also known as clumped isotopes. Currently, we are investigating the potential of these novel iso- topic tracers to track the complex N O production and consumption pathways. Improved understanding of the 2 nitrogen cycle will be a major step towards N O emission reduction. 2 Keywords: Biogeochemical nitrogen cycle · Clumped isotopes · Greenhouse gas · Laser spectroscopy · Nitrous oxide Kristýna Kantnerová was born in the Czech billion, 10-9 moles of trace gas per mole of dry air)in the preindus- Republic in 1991. In 2016, she obtained her trial era (before 1750)[4] to 329.9 ± 0.1 ppb in 2017,[5] and the in- Master’s degree in Analytical Chemistry crease steadily continues. Developing mitigation options for this and Quality Engineering from University trace gas requires a profound understanding of its biogeochemical of Chemistry and Technology, Prague with cycle and control parameters. honors. She conducted her Master’s thesis Although the global N O budget and the main source areas – 2 in the Molecular Electrochemistry group soils under natural vegetation, agricultural land use, and oceans – at the J. Heyrovsky Institute of Physical are well known, fluxes exhibit very high spatial and temporal vari- Chemistry. Since 2016, she is in the group ability, which makes predictions and mitigation very challenging. of Dr. Joachim Mohn at Empa Dübendorf In addition, the specific biogeochemical production pathways of and in the group of Prof. Stefano Bernasconi at ETH Zürich. N O display a high complexity, with many potential microbial and 2 Her PhD work is focused on developing a quantum cascade laser abiotic transformations. A detailed description of processes known based analytical technique for the analysis of the doubly substi- to lead to N O formation or consumption and of challenges in their 2 tuted (‘clumped’) isotopic species of nitrous oxide and exploring characterization can be found in a number of review articles.[6,7] their usage. Currently, the most important pathways in soils are considered to be: bacterial heterotrophic denitrification and nitrifier-denitrifi- 1. Introduction cation, nitrification, and chemodenitrification. However, as some Mitigating anthropogenic emissions of greenhouse gases of these processes start from the same substrates (e.g. nitrates or (GHG) into the Earth’s atmosphere is one of the biggest chal- nitrites), and even exhibit the same reaction intermediates, quanti- lenges that the scientific community and the society in general fication of their individual contributions is still not possible. is currently facing. Emissions of nitrous oxide, N O, contribute In this context, natural abundance stable isotope signatures 2 to global warming by 6%[1] due to its strong global warming po- can be used as fingerprints to trace transformations of sub- tential, which is 300 times higher than that of CO .[2] In addition, stances present in the environment. Likewise, the stable iso- 2 N O is the most important anthropogenically emitted substance topic composition of GHG, such as N O, provides important 2 2 responsible for the depletion of stratospheric ozone.[3] Its atmo- information about source and sink processes.[8,9] The natural spheric abundance has increased from around 270 ppb (parts-per- variations in stable isotope abundances are due to the fact that *Correspondence: Dr. J. Mohna E-mail: [email protected] aLaboratory for Air Pollution / Environmental Technology, Empa – Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, CH-8600 Dübendorf; bGeological Institute, Department of Earth Sciences, ETH Zürich, Sonneggstrasse 5, CH-8092 Zürich Laureates: Junior Prizes of the sCs faLL Meeting 2018 CHIMIA 2019, 73, No. 4 233 in many biotic and abiotic processes, the reaction rates dif- fer between isotopic species, e.g. reduction of 15NO – versus 2 14NO –, leading to a so-called isotopic fractionation.[10] As the 2 isotopic fractionation is distinct for certain reaction pathways, this information can be used to differentiate source processes from each other. The N O molecule (N=N=O) involves in total 2 12 distinct ‘isotopically substituted molecules’ or ‘isotopoc- ules’, representing all possible combinations of the nitrogen isotopes 14N and 15N and the oxygen isotopes 16O, 17O, and 18O. The term ‘isotopocule’ is an umbrella term of ‘isopologue’ and ‘isotopomer’ (isotopic isomer).A particular feature for the asymmetric N O molecule is that the central (α, N*NO) and the 2 end (β, *NNO) N atom are distinguishable, which has particular potential for source attribution as discussed below. A list of all N O isotopocules together with their average abundance and 2 molecular mass can be found in Table 1. The abundance of iso- topocules is usually reported in the δ notation and the deviation from a reference standard expressed in ‰ values: = −1 (1) = − (2) Fig. 1. Dual isotopocule mapping approach with isotopic signatures of several biotic and abiotic sources of N O (adapted from refs [13,15]). 2 where X denotes e.g. 15Nα, 15Nβ, 15Nbulk (for average 15N content), R is the ratio between the amount fraction of the rare isotopic spe- not only by the reaction through which it is produced but also cies and the amount fraction of most abundant species 14N14N16O, by the composition of the substrate. In contrast, the difference e.g. R(15N14N16O/14N14N16O) = x(15N14N16O)/x(14N14N16O), for the between 15N substitution in α and β position, SP, is independent sample and the reference gas.[11] The difference between 15N sub- from the isotopic composition of the precursor and therefore of stitution in α and β position, defined according to Eqn. (2), is particular interest to differentiate biogeochemical reaction path- denoted as site preference (SP). Reference standards provide the ways in the nitrogen cycle.[13] Generally, there is a stronger affin- link to the international scale for isotope ratios, which is atmo- ity of 15N towards the central than towards the end N position in spheric N (Air-N ) for nitrogen isotopes and Vienna Standard the N O molecule, due to a lower zero-point energy of 14N15N1xO 2 2 2 Mean Ocean Water (VSMOW) for oxygen isotopes.[12] as compared to 15N14N1xO.[14] While isotopocule mapping has In the dual N O isotopocule mapping approach, isotope sig- shown potential to study individual reactions, in particular if 2 natures are combined to allocate source processes (Fig. 1). The additional supporting parameters or modelling approaches are bulk isotopic composition of N O (δ15Nbulk, δ18O) is influenced available, overlapping isotopocule signatures often prevent a 2 quantitative assignment. Theoretical predictions indicate that multiply substituted, so- Table 1. The N O isotopocules, their natural average abundance, and 2 called ‘clumped’ isotopocules, provide additional constraints on molecular masses. For the multiply substituted isotopic species, random reaction pathways. Under equilibrium conditions, clumping of (stochastic) distribution of isotopes among all isotopocules is assumed. heavier isotopes in a chemical bond is thermodynamically favor- able because ‘heavier’ chemical bonds are more stable.[16] The isotopocule relative mass m(X)/u extent of this phenomenon is temperature-dependent, meaning abundance that the abundance of ‘clumped isotopes’ in a sample bears in- 14N14N16O9.903·10–1 44.0011 formation about the equilibrium formation temperature and the reversibility of a process.[17–19] In carbonate paleothermometry, 14N15N16O3.641·10–3 44.9981 this formalism is used to study past climate on Earth.[20–23] Under non-equilibrium kinetic conditions, the clumped signature pro- 15 14 16 –3 N N O3.641·10 44.9981 vides information on the reversibility of a reaction and thus ad- 14N14N18O1.986·10–3 46.0053 ditional dimensionality for interpretation.[24] Apart from their use in source studies, clumped N O isotopes have been suggested as 2 14N14N17O3.762·10–4 45.0053 powerful tracers for the main sink process, stratospheric photoly- sis.[25] Concentrations of clumped isotopic species are given in 15 15 16 –5 N N O1.339·10 45.9951 the ∆ notation: 14N15N18O7.300·10–6 47.0023 15 14 18 –6 N N O7.300·10 47.0023 ∆556 = −1 − −1 − −1 (3) 14N15N17O1.383·10–6 46.0023 15N14N17O1.383·10–6 46.0023 where R556, R456, R546 are the abundance ratios of the isoto- pocules 15N15N16O, 14N15N16O, and 15N14N16O relative to 14N14N16O, 15N15N18O2.684·10–8 47.9994 in the sample and in a reference gas with stochastic (random) isotopic composition. SP18 is defined as the difference between 15N15N17O5.085·10–9 46.9993 ∆458 and ∆548. 234 CHIMIA 2019, 73, No. 4 Laureates: Junior Prizes of the sCs faLL Meeting 2018 Traditionally, isotopocules of N O are analyzed by iso- ity for the low abundant N O isotopocules (e.g.
Load more

Recommended publications
  • Geochemistry and Petrology of Listvenite in the Samail Ophiolite, Sultanate of Oman: Complete Carbonation of Peridotite During Ophiolite Emplacement
    Available online at www.sciencedirect.com ScienceDirect Geochimica et Cosmochimica Acta 160 (2015) 70–90 www.elsevier.com/locate/gca Geochemistry and petrology of listvenite in the Samail ophiolite, Sultanate of Oman: Complete carbonation of peridotite during ophiolite emplacement Elisabeth S. Falk ⇑, Peter B. Kelemen Lamont-Doherty Earth Observatory, Columbia University, Palisades, NY 10964, USA Received 16 May 2014; accepted in revised form 14 March 2015; available online 20 March 2015 Abstract Extensive outcrops of listvenite—fully carbonated peridotite, with all Mg in carbonate minerals and all Si in quartz—occur along the basal thrust of the Samail ophiolite in Oman. These rocks can provide insight into processes including (a) carbon fluxes at the “leading edge of the mantle wedge” in subduction zones and (b) enhanced mineral carbonation of peridotite as a means of carbon storage. Here we examine mineralogical, chemical and isotopic evidence on the temperatures, timing, and fluid compositions involved in the formation of this listvenite. The listvenites are composed primarily of magnesite and/or dolomite + quartz + relict Cr-spinel. In some instances the conversion of peridotite to listvenite is nearly isochemical except for the addition of CO2, while other samples have also seen significant calcium addition and/or variable, minor addition of K and Mn. Along margins where listvenite bodies are in contact with serpentinized peridotite, talc and antigorite are present in addition to carbonate and quartz. The presence of antigorite + quartz + talc in these samples implies temperatures of 80– 130 °C. This range of temperature is consistent with dolomite and magnesite clumped isotope thermometry in listvenite (aver- age T = 90 ± 15 °C) and with conventional mineral-water oxygen isotope exchange thermometry (assuming fluid d18O near zero).
    [Show full text]
  • Download High-Res Image (262KB) 2
    UC Berkeley UC Berkeley Previously Published Works Title Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes Permalink https://escholarship.org/uc/item/5dm6b94h Authors Stolper, DA Eiler, JM Publication Date 2016-05-15 DOI 10.1016/j.gca.2016.02.030 Peer reviewed eScholarship.org Powered by the California Digital Library University of California Constraints on the formation and diagenesis of phosphorites using carbonate clumped isotopes Author links open overlay panel Daniel A.Stolper a1 John M.Eiler a Show more https://doi.org/10.1016/j.gca.2016.02.030 Get rights and content Abstract The isotopic composition of apatites from sedimentary phosphorite deposits has been used previously to reconstruct ancient conditions on the surface of the Earth. However, questions remain as to whether these minerals retain their original isotopic composition or are modified during burial and lithification. To better understand how apatites in phosphorites form and are diagenetically modified, we present new isotopic 18 measurements of δ O values and clumped-isotope-based (Δ47) temperatures of carbonate groups in apatites from phosphorites from the past 265 million years. We compare these measurements to previously measured δ18O values of phosphate groups from the same apatites. These results indicate that the isotopic composition of many of the apatites do not record environmental conditions during formation but instead diagenetic conditions. To understand these results, we construct a model that describes the consequences of diagenetic modification of phosphorites as functions of the environmental conditions (i.e., temperature and δ18O values of the fluids) during initial precipitation and subsequent diagenesis.
    [Show full text]
  • Carbonate Clumped Isotope (47) Evidence from the Tornillo Basin, Te
    Paleoceanography and Paleoclimatology RESEARCH ARTICLE Warm Terrestrial Subtropics During the Paleocene and Eocene: 10.1029/2018PA003391 Carbonate Clumped Isotope (Δ47) Evidence From the Tornillo Special Section: Basin, Texas (USA) Climatic and Biotic Events of the Paleogene: Earth Systems Julia R. Kelson1 , Dylana Watford2, Clement Bataille3 , Katharine W. Huntington1 , and Planetary Boundaries in a Ethan Hyland4 , and Gabriel J. Bowen2 Greenhouse World 1Department of Earth and Space Sciences and Quaternary Research Center, University of Washington, Seattle, WA, USA, 2 3 Key Points: Department of Geology and Geophysics, University of Utah, Salt Lake City, UT, USA, Department of Earth and • Paleosol carbonate nodules from the Environmental Sciences, University of Ottawa, Ottawa, ON, Canada, 4Department of Marine, Earth, and Atmospheric Tornillo Basin record primary Sciences, NC State University, Raleigh, NC, USA environmental values of carbon, oxygen, and clumped isotopes • Carbonate nodules record average Abstract Records of subtropical climate on land from the early Paleogene offer insights into how the Earth clumped isotope temperatures of 25 ± 4 and 32 ± 2 °C for the system responds to greenhouse climate conditions. Fluvial and floodplain deposits of the Tornillo Basin (Big Paleocene and early Eocene, Bend National Park, Texas, USA) preserve a record of environmental and climatic change of the Paleocene respectively and the early Eocene. We report carbon, oxygen, and clumped isotopic compositions (δ13C, δ18O, and Δ )of • These temperature estimates are 47 lower than model predictions, and paleosol carbonate nodules from this basin. Mineralogical, geochemical, and thermal modeling evidence data-model discrepancies remain at suggests that the measured isotopic values preserve primary environmental signals with a summer bias with low latitudes for the Eocene the exception of data from two nodules reset by local igneous intrusions.
    [Show full text]
  • Carbonate Clumped Isotope Thermometry in Continental Tectonics
    Tectonophysics 647–648 (2015) 1–20 Contents lists available at ScienceDirect Tectonophysics journal homepage: www.elsevier.com/locate/tecto Invited Review Carbonate clumped isotope thermometry in continental tectonics Katharine W. Huntington a,⁎, Alex R. Lechler a,b a Department of Earth and Space Sciences, University of Washington, Johnson Hall Rm-070, Box 351310, 4000 15th Avenue NE, Seattle, WA 98195-1310, United States b Department of Geosciences, Pacific Lutheran University, Rieke Rm-158, Tacoma, WA 98447-0003, United States article info abstract Article history: Reconstructing the thermal history of minerals and fluids in continental environments is a cornerstone of tecton- Received 22 July 2014 ics research. Paleotemperature constraints from carbonate clumped isotope thermometry have provided impor- Received in revised form 18 December 2014 tant tests of geodynamic, structural, topographic and basin evolution models. The thermometer is based on the Accepted 22 February 2015 13 18 C– O bond ordering in carbonates (mass-47 anomaly, Δ47) and provides estimates of the carbonate formation Available online 28 February 2015 18 temperature independent of the δ O value of the water from which the carbonate grew; Δ47 is measured δ13 δ18 Keywords: simultaneously with conventional measurements of carbonate Cand O values, which together constrain Clumped isotope thermometry the isotopic composition of the parent water. Depending on the geologic setting of carbonate growth, this infor- Carbonate mation can help constrain paleoenvironmental conditions or basin temperatures and fluid sources. This review Paleoelevation examines how clumped isotope thermometry can shed new light on problems in continental tectonics, focusing Digenesis on paleoaltimetry, basin evolution and structural diagenesis applications.
    [Show full text]
  • Clumped Isotope Thermometry of Carbonatites As an Indicator of Diagenetic Alteration
    Available online at www.sciencedirect.com Geochimica et Cosmochimica Acta 74 (2010) 4110–4122 www.elsevier.com/locate/gca Clumped isotope thermometry of carbonatites as an indicator of diagenetic alteration Kate J. Dennis *, Daniel P. Schrag Department of Earth and Planetary Sciences, Harvard University, 20 Oxford Street, Cambridge, MA 02138, USA Received 16 September 2009; accepted in revised form 6 April 2010; available online 24 April 2010 Abstract We measure the clumped isotopic signature of carbonatites to assess the integrity of the clumped isotope paleothermometer over long timescales (107–109 years) and the susceptibility of the proxy to closed system re-equilibration of isotopes during burial diagenesis. We find pristine carbonatites that have primary oxygen isotope signatures, along with a Carrara marble standard, do not record clumped isotope signatures lighter than 0.31& suggesting atoms of carbon and oxygen freely exchange within the carbonate lattice at temperatures above 250–300 °C. There is no systematic trend in the clumped isotope signature of pristine carbonatites with age, although partial re-equilibration to lower temperatures can occur if a carbonatite has been exposed to burial temperatures for long periods of time. We conclude that the solid-state re-ordering of carbon and oxygen atoms is sufficiently slow to enable the use of clumped isotope paleothermometry on timescales of 108 years, but that diagenetic resetting can still occur, even without bulk recrystallization. In addition to the carbonatite data, an inorganic cal- ibration of the clumped isotope paleothermometer for low temperature carbonates (7.5–77 °C) is presented and highlights the need for further inter-lab standardization.
    [Show full text]
  • Aptian-Albian Clumped Isotopes from Northwest China: Cool Temperatures, Variable Atmospheric Pco2 and Regional Shifts in Hydrologic Cycle Dustin T
    https://doi.org/10.5194/cp-2020-152 Preprint. Discussion started: 21 December 2020 c Author(s) 2020. CC BY 4.0 License. Aptian-Albian clumped isotopes from northwest China: Cool temperatures, variable atmospheric pCO2 and regional shifts in hydrologic cycle Dustin T. Harper1, Marina B. Suarez1,2, Jessica Uglesich2, Hailu You3,4,5, Daqing Li6, Peter Dodson7 5 1 Department of Geology, The University of Kansas, Lawrence, KS, U.S.A. 2 Department of Geological Sciences, University of Texas, San Antonio, TX, U.S.A. 3 Key LaBoratory of VerteBrate Evolution and Human Origins, Institute of VerteBrate Paleontology and Paleoanthropology, Chinese Academy of Sciences, Beijing, P.R.C. 10 4 Chinese Academy of Science Center for Excellence in Life and Paleoenvironment, Beijing, P.R.C. 5 College of Earth and Planetary Sciences, University of Chinese Academy of Sciences, Beijing, P.R.C. 6 Institute of VerteBrate Paleontology and College of Life Science and Technology, Gansu Agricultural University, Lanzhou, P.R.C. 7 Department of Biomedical Sciences, The University of Pennsylvania, Philadelphia, U.S.A. 15 Correspondence to: Dustin T. Harper ([email protected]) Abstract. The Early Cretaceous is characterized by warm background temperatures (i.e., greenhouse climate) and carbon cycle perturbations that are often marked by Ocean Anoxic Events (OAEs) and associated shifts in the hydrologic cycle. Higher-resolution records of terrestrial and marine δ13C and δ18O (Both carBonates and organics) suggest climate shifts 20 during the Aptian-AlBian, including a warm period associated with OAE 1a in the early Aptian and subsequent “cold snap” near the Aptian-AlBian Boundary prior to the Kilian and OAE 1B.
    [Show full text]
  • Chapter 1 Carbonate Clumped Isotopes In
    1 Chapter 1 Carbonate clumped isotopes in sedimentary rocks: Insights from the Sultanate of Oman Kristin D. Bergmann1, Said Al Balushi2, John P. Grotzinger1, John M. Eiler1 1California Institute of Technology 2Petroleum Development Oman 1.1 Abstract While the field of carbonate clumped isotope thermometry has grown dramati- cally since its recent inception [1, 2, 3, 4], there remains considerable uncertainty regarding its usefulness in questions of deep time. This is in large part because questions remain regarding the impact of burial on the isotopic ordering within the carbonate crystal lattice. There is evidence that both recrystallization and solid state diffusion within the crystal lattice are important processes [5, 6, 3, 7, 8]. Yet the time and depth dependence of these processes remains poorly constrained in natural samples. This study explores how the burial and exhumation history mod- ifies the primary ordering of 13C and 18O in carbonates from the subsurface and surface of Oman. The study suite includes carbonates of Eocene to Neoproterozoic age that sit at current burial depths of 350 m to 5850 m. We can directly compare the measured clumped isotope temperatures to current borehole temperatures and 2 the petrography of core samples. Additionally, we analyzed exhumed carbonates from the same formations, estimated to have been buried from 1{2 km up to 8{10 km. Results indicate two dominant modes of diagenesis within the shallow burial environment (< 6 km) that are independent of burial depth. These modes have specific temperatures in clumped isotope space as well as in reconstructed water 18 space, calculated from the measured clumped isotope temperature and δ Omin.
    [Show full text]
  • Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer
    View metadata, citation and similar papers at core.ac.uk brought to you by CORE provided by Caltech Authors Accepted Manuscript Review Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer Peter M.J. Douglas, Daniel A. Stolper, John M. Eiler, Alex L. Sessions, Michael Lawson, Yanhua Shuai, Andrew Bishop, Olaf G. Podlaha, Alexandre A. Ferreira, Eugenio V. Santos Neto, Martin Niemann, Arne S. Steen, Ling Huang, Laura Chimiak, David L. Valentine, Jens Fiebig, Andrew J. Luhmann, William E. Seyfried Jr., Giuseppe Etiope, Martin Schoell, William P. Inskeep, James J. Moran, Nami Kitchen PII: S0146-6380(17)30347-9 DOI: http://dx.doi.org/10.1016/j.orggeochem.2017.07.016 Reference: OG 3592 To appear in: Organic Geochemistry Received Date: 26 June 2017 Revised Date: 11 July 2017 Accepted Date: 22 July 2017 Please cite this article as: Douglas, P.M.J., Stolper, D.A., Eiler, J.M., Sessions, A.L., Lawson, M., Shuai, Y., Bishop, A., Podlaha, O.G., Ferreira, A.A., Santos Neto, E.V., Niemann, M., Steen, A.S., Huang, L., Chimiak, L., Valentine, D.L., Fiebig, J., Luhmann, A.J., Seyfried, W.E. Jr., Etiope, G., Schoell, M., Inskeep, W.P., Moran, J.J., Kitchen, N., Methane Clumped Isotopes: Progress and Potential for a New Isotopic Tracer, Organic Geochemistry (2017), doi: http://dx.doi.org/10.1016/j.orggeochem.2017.07.016 This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form.
    [Show full text]
  • The Application of Silica Δ'17o and Δ18o Towards Paleo- Environmental Reconstructions
    The application of silica Δ'17O and δ18O towards paleo- environmental reconstructions The Harvard community has made this article openly available. Please share how this access benefits you. Your story matters Citation Liljestrand, Frasier. 2019. The application of silica Δ'17O and δ18O towards paleo-environmental reconstructions. Doctoral dissertation, Harvard University, Graduate School of Arts & Sciences. Citable link http://nrs.harvard.edu/urn-3:HUL.InstRepos:42013151 Terms of Use This article was downloaded from Harvard University’s DASH repository, and is made available under the terms and conditions applicable to Other Posted Material, as set forth at http:// nrs.harvard.edu/urn-3:HUL.InstRepos:dash.current.terms-of- use#LAA 0 The application of silica Δ 17O and δ18O towards paleo-environmental reconstructions a dissertation presented by Frasier L. Liljestrand to The Department of Earth and Planetary Sciences in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the subject of Earth and Planetary Sciences Harvard University Cambridge, Massachusetts August 2019 © 2019 - Frasier L. Liljestrand All rights reserved. Thesis advisor: David T. Johnston Frasier L. Liljestrand 0 The application of silica Δ 17O and δ18O towards paleo-environmental reconstructions Abstract The oxygen isotope composition of silica provides a valuable record of the temperature at which it precipitated and the isotopic composition of the fluid 18 with which it equilibrated. This temperature-δ OH2O pair, however, is non-unique. The chert δ18O record shows a robust quasi-linear increase through time, but this signal has been interpreted as reflecting either cooling oceans, 0 shifting marine δ18O composition, or diagenesis.
    [Show full text]
  • Evaluation of Kinetic Effects on Clumped Isotope Fractionation (О”47) During Inorganic Calcite Precipitation
    Available online at www.sciencedirect.com ScienceDirect Geochimica et Cosmochimica Acta 134 (2014) 120–136 www.elsevier.com/locate/gca Evaluation of kinetic effects on clumped isotope fractionation (D47) during inorganic calcite precipitation Jianwu Tang a,⇑, Martin Dietzel b, Alvaro Fernandez a, Aradhna K. Tripati c,d, Brad E. Rosenheim a,1 a Department of Earth & Environmental Sciences, Tulane University, New Orleans, LA 70118-5698, USA b Institute of Applied Geosciences, Graz University of Technology, Rechbauerstrasse 12, 8010 Graz, Austria c Department of Earth and Space Sciences, Institute of Geophysics and Planetary Physics, University of California, Los Angeles, CA 90095, USA d Department of Atmospheric and Oceanic Sciences, Institute of the Environment and Sustainability, University of California, Los Angeles, CA 90095, USA Received 17 September 2013; accepted in revised form 4 March 2014; available online 24 March 2014 Abstract 13 18 Considerable efforts have been made to calibrate the D47 paleothermometer, which derives from the quantity of C– O bonds in carbon dioxide produced during acid digestion of carbonate minerals versus its expected stochastic abundance, in a range of materials. However the impacts of precipitation rate, ionic strength, and pH on carbonate D47 values are still unclear. Here we present a set of 75 measurements of D47 values from inorganic calcites grown under well-controlled experimental 2 conditions, where we evaluate the impact on D47 values of precipitation rate (logR = 1.8–4.4 lmol/m /h), pH (8.3–10.5; NBS pH scale), and ionic strength (I = 35–832 mM). With the data available and at the current instrumental resolution, our study does not resolve any clear effects of pH, ionic strength, growth rate effects on measured D47 when compared in mag- nitude to the effects on d18O over most of the ranges of parameters sampled by our analyses.
    [Show full text]
  • Effects of Brine Chemistry and Polymorphism on Clumped Isotopes
    Available online at www.sciencedirect.com ScienceDirect Geochimica et Cosmochimica Acta 160 (2015) 155–168 www.elsevier.com/locate/gca Effects of brine chemistry and polymorphism on clumped isotopes revealed by laboratory precipitation of mono- and multiphase calcium carbonates Tobias Kluge ⇑,1,Ce´dric M. John Department of Earth Science and Engineering and Qatar Carbonate and Carbon Storage Research Centre, Imperial College London, Prince Consort Road, London, SW7 2BP, UK Received 7 October 2014; accepted in revised form 29 March 2015; Available online 4 April 2015 Abstract Carbonate clumped isotopes are applied to an increasing number of geological archives to address a wide range of Earth science questions. However, the effect of changes in salinity on the carbonate clumped isotope technique has not been inves- tigated experimentally yet. In particular, evaporated sea water and diagenetic fluids differ substantially from solutions used to calibrate the clumped isotope thermometer as they exhibit high ionic concentrations of e.g., Na+,Ca2+,Mg2+, and ClÀ. High ionic concentrations are known to have an impact on d18O values, and could potentially impact the successful application of clumped isotopes to the reconstruction of diagenetic processes, including precipitation temperatures and the origin of the diagenetic fluid. In order to address the potential influence of salt ions on the clumped isotope D47 value we precipitated CaCO3 minerals (calcite, aragonite and vaterite), hydromagnesite and mixtures of these minerals in the laboratory from solutions containing different salt ions (Na+,Ca2+,Mg2+,ClÀ) at various concentrations and temperatures. The precipitation of some mineralogies was restricted to solutions with specific ionic concentrations, limiting direct comparability.
    [Show full text]
  • 5 International Clumped Isotope Workshop
    5th International Clumped Isotope Workshop St Petersburg Florida University of South Florida January 6th to 9th, 2015 Page 001 Variable D47 acid digestion fractionation Hagit P. Affek1 1 The Institute of Earth Sciences, The Hebrew University of Jerusalem, Israel. Email: [email protected] The extraction of CO2 from CaCO3 via digestion by phosphoric acid includes a fractionation 18 factor that affects both d O and D47. In both systems the fractionation factor is assumed to vary only with temperature and to be constant at a specific temperature. A correction factor is therefore derived to enable comparison of data that is produced under different acid digestion temperatures, reflecting the difference between 25°C reaction and a reaction at a higher temperature (Dd25-T). Calcite samples having a wide range of D47 values (0.26‰ - 0.74‰) and of bulk composition (d47 values between -40‰ and +20‰) were analyzed using acid digestion at either 25°C or 90°C. The difference in D47 values when digesting at 90°C versus 25°C (Dd25- 90) is highly variable, suggesting that the acid digestion fractionation is not constant at a given temperature. Dd25-90 varies between the accepted value of 0.09‰ to as low as 0.03‰, and correlates with the bulk isotopic composition of the sample (either d47 of the sum of d13C+d18O). This strong variability is observed in particular when phosphoric acid concentration is at the low end of commonly used concentrations (103%); weaker variability is observed when using higher acid concentration (105%). Such non-constant Dd25-90 leads to potential systematic errors in D47 determination in experimental setups in which acid concentration is relatively low, or if concentrations change over time, as may often be the case in a common acid bath.
    [Show full text]