Assessment of factors controlling clumped isotopes and delta O-18 values of hydrothermal vent calcites
File(s)
Author(s)
Kluge, Tobias
John, Cedric M
Boch, Ronny
Kele, Sandor
Type
Journal Article
Abstract
The clumped isotope composition of CaCO3 (Δ47) is a geochemical proxy that can provide mineral formation temperatures and, together with measured carbonate δ18O, inferred fluid δ18O values. Under natural conditions, carbonates form within a relatively wide pH range and varying growth rates which are typically not reflected in laboratory‐based calibrations (mostly ∼pH 8, moderate growth rates). A pH and growth‐rate dependence is known for oxygen isotopes and was also postulated for clumped isotopes. Theoretical predictions suggest that Δ47 values could lie between the carbonate equilibrium value and the value inherited from the dissolved inorganic carbon (predicted offset: +0.04‰ pH < 4 and −0.025‰ at high pH > 12). Here we test whether pH (in addition to temperature) is recorded in the carbonate clumped isotope composition using modern calcites from natural travertine‐forming streams and scales precipitated in pipes of deep geothermal wells from Italy, Hungary, and Turkey (pH: 6.1–7.5, T: 33–100°C). Although a comparison of all samples with expected equilibrium values in this pH range and known formation temperatures reveals only an insignificant Δ47 offset (0.006 ± 0.004‰, 1SE, n = 9), the clumped isotope values of samples with the highest growth rates (0.014 ± 0.007‰, 1SE, n = 5) are consistent with the theoretical prediction attributable to pH of 0.01‰. Similarly, deviations in δ18O of up to −2‰ follow a growth‐rate dependence. This field‐based study shows that pH‐related effects are mostly small for Δ47 in the subsurface environment at lower pH and that high mineral growth rates control the magnitude of this disequilibrium.
Date Issued
2018-06-01
Date Acceptance
2018-04-17
Citation
Geochemistry, Geophysics, Geosystems, 2018, 19 (6), pp.1844-1858
ISSN
1525-2027
Publisher
American Geophysical Union
Start Page
1844
End Page
1858
Journal / Book Title
Geochemistry, Geophysics, Geosystems
Volume
19
Issue
6
Copyright Statement
© 2018 American Geophysical Union. All Rights Reserved.
Sponsor
Qatar Petroleum
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000445194000009&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Grant Number
N/A
Subjects
Science & Technology
Physical Sciences
Geochemistry & Geophysics
DISSOLVED INORGANIC CARBON
TEMPERATURE-DEPENDENCE
C-13-O-18 BONDS
GROWTH-RATE
IN-SITU
EQUILIBRIUM FRACTIONATION
DEPOSITIONAL FACIES
CAVE SPELEOTHEMS
ULTRAMAFIC ROCKS
OXYGEN ISOTOPES
Publication Status
Published
Date Publish Online
2018-04-27