The influence of temperature and seawater carbonate saturation state on &amp;lt;sup&amp;gt;13&amp;lt;/sup&amp;gt;C-&amp;lt;sup&amp;gt;18&amp;lt;/sup&amp;gt;O bond ordering in bivalve mollusks

Eiler, John M.; Tripati, Aradhna; Ries, Justin B.; Hiebenthal, Claas; Taviani, Marco; Elliot, Mary; Marenssi, Sergio A.; Nakamura, Kenji; Ramírez, Pedro Dueñas; Roy, Kaustuv

doi:10.5194/bgd-10-157-2013

Cited by 44 publications

(74 citation statements)

References 62 publications

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“…2) (23), supporting previous findings (24,25) that the relationship between molluscan carbonate growth temperature and Δ 47 agrees with inorganic calcite calibration data. Some recently published clumped isotope analyses of modern bivalve shells have suggested the possibility of significant deviations from the synthetic-calcite calibration (26)(27)(28). The reason for these deviations is unknown at present, but is likely to be at least in part due to interlaboratory methodological differences, possibly related to the temperature of acid digestion (28).…”

Section: Resultsmentioning

confidence: 99%

Pronounced zonal heterogeneity in Eocene southern high-latitude sea surface temperatures

Douglas

Affek

Ivany

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

151

203

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Paleoclimate studies suggest that increased global warmth during the Eocene epoch was greatly amplified at high latitudes, a state that climate models cannot fully reproduce. However, proxy estimates of Eocene near-Antarctic sea surface temperatures (SSTs) have produced widely divergent results at similar latitudes, with SSTs above 20°C in the southwest Pacific contrasting with SSTs between 5 and 15°C in the South Atlantic. Validation of this zonal temperature difference has been impeded by uncertainties inherent to the individual paleotemperature proxies applied at these sites. Here, we present multiproxy data from Seymour Island, near the Antarctic Peninsula, that provides well-constrained evidence for annual SSTs of 10-17°C (1σ SD) during the middle and late Eocene. Comparison of the same paleotemperature proxy at Seymour Island and at the East Tasman Plateau indicate the presence of a large and consistent middle-to-late Eocene SST gradient of ∼7°C between these two sites located at similar paleolatitudes. Intermediate-complexity climate model simulations suggest that enhanced oceanic heat transport in the South Pacific, driven by deep-water formation in the Ross Sea, was largely responsible for the observed SST gradient. These results indicate that very warm SSTs, in excess of 18°C, did not extend uniformly across the Eocene southern high latitudes, and suggest that thermohaline circulation may partially control the distribution of high-latitude ocean temperatures in greenhouse climates. The pronounced zonal SST heterogeneity evident in the Eocene cautions against inferring past meridional temperature gradients using spatially limited data within given latitudinal bands.paleooceanography | clumped isotopes | organic geochemistry | climate modeling | high-latitude climate

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Section: Resultsmentioning

confidence: 99%

Pronounced zonal heterogeneity in Eocene southern high-latitude sea surface temperatures

Douglas

Affek

Ivany

et al. 2014

Proc. Natl. Acad. Sci. U.S.A.

151

203

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“…Differences in the temperature-D 47 calibrations for inorganic calcite reported by Ghosh et al (2006) and Dennis and Schrag (2010) could partially reflect pH effects. It is possible that some of the systematic scatter observed in biogenic calibration data may also arise from pH Tripati et al, 2010;Thiagarajan et al, 2011;Eagle et al, 2013). Future studies may show there are systematic environmental and biological differences in calibrations between taxa originating from DIC speciation effects.…”

Section: Discussionmentioning

confidence: 99%

“…However, disequilibrium clumped isotopic signatures have been reported, first in warm-water aragonitic corals and subsequently in other biogenic carbonates Thiagarajan et al, 2011;Eagle et al, 2013;Saenger et al, 2012), as well as speleothems (Affek et al, 2008;Daeron et al, 2011). Unrecognized anomalous signatures from disequilibrium conditions can potentially cause errors of several degrees Celsius in the estimation of temperatures and need to be addressed to avoid jeopardizing the reliability of clumping as a temperature proxy (e.g., Ghosh et al, 2006;Daeron et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

Theoretical constraints on the effects of pH, salinity, and temperature on clumped isotope signatures of dissolved inorganic carbon species and precipitating carbonate minerals

Hill

Tripati

Schauble

2014

Geochimica et Cosmochimica Acta

145

194

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The use of carbonate 'clumped isotope' thermometry as a geochemical technique to determine temperature of formation of a carbonate mineral is predicated on the assumption that the mineral has attained an internal thermodynamic equilibrium. If true, then the clumped isotope signature is dependent solely upon the temperature of formation of the mineral without the need to know the isotopic or elemental composition of coeval fluids. However, anomalous signatures can arise under disequilibrium conditions that can make the estimation of temperatures uncertain by several degrees Celsius. Here we use ab initio calculations to examine the potential disequilibrium mineral signatures that may arise from the incorporation of dissolved inorganic carbon (DIC) species (predominantly aqueous carbonate and bicarbonate ions) into growing crystals without full equilibration with the crystal lattice.We explore theoretically the nature of clumping in the individual DIC species and the composite DIC pool under varying pH, salinity, temperature, and isotopic composition, and speculate about their effects upon the resultant disequilibrium clumping of the precipitates. We also calculate equilibrium clumped signatures for the carbonate minerals calcite, aragonite, and witherite. Our models indicate that each DIC species has a distinct equilibrium clumped isotope signature such that, (witherite). We define the calcite clumped crossover pH as the pH at which the composite D 47 (DIC pool) = D 47 (equilibrium calcite). If disequilibrium D 47 (calcite) is misinterpreted as equilibrium D 47 (calcite), it is possible to overestimate or underestimate the growth temperature by small but significant amounts. Increases in salinity lower the clumped crossover pH and may cause larger effects. Extreme effects of pH, salinity, and temperature, such as between cold freshwater lakes at high latitudes to hot hypersaline environments, are predicted to have sizeable effects on the clumped isotope composition of aqueous DIC pools.In order to determine the most reliable and efficient modeling methods to represent aqueous dissolved inorganic carbon (DIC) species and carbonate minerals, we performed convergence and sensitivity testing on several different levels of theory. We used 4 different techniques for modeling the hydration of DIC: gas phase, implicit solvation (PCM and SMD), explicit solvation (ion with 3 water molecules) and supermolecular clusters (ion plus 21 to 32 water molecules with geometries generated by molecular dynamics). For each solvation technique, we performed sensitivity testing by combining different levels of theory (up to 8 ab initio/hybrid methods, each with up to 5 different sizes of basis sets) to understand the limits of each technique. We looked at the degree of convergence with the most complex (and accurate) models in order to select the most reliable and efficient modeling methods. The B3LYP method combined with the 6-311++G(2d,2p) basis set with supermolecular clusters worked well.

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“…An acid digestion fractionation of 0.092‰ was applied to derive the clumped isotope composition of all carbonate standards and samples reported here (58). Clumped isotope temperatures were calculated using a revised temperature calibration equation based on inorganically precipitated calcites (38,39). The oxygen isotope composition of the fluid from which these vein calcites precipitated were calculated based on the oxygen isotope composition of calcite and the clumped isotope temperatures (40).…”

Section: Methodsmentioning

confidence: 99%

Fluid mixing and the deep biosphere of a fossil Lost City-type hydrothermal system at the Iberia Margin

Klein

Humphris

Guo

et al. 2015

Proc. Natl. Acad. Sci. U.S.A.

100

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Subseafloor mixing of reduced hydrothermal fluids with seawater is believed to provide the energy and substrates needed to support deep chemolithoautotrophic life in the hydrated oceanic mantle (i.e., serpentinite). However, geosphere-biosphere interactions in serpentinite-hosted subseafloor mixing zones remain poorly constrained. Here we examine fossil microbial communities and fluid mixing processes in the subseafloor of a Cretaceous Lost City-type hydrothermal system at the magma-poor passive Iberia Margin (Ocean Drilling Program Leg 149, Hole 897D). Brucite−calcite mineral assemblages precipitated from mixed fluids ca. 65 m below the Cretaceous paleo-seafloor at temperatures of 31.7 ± 4.3°C within steep chemical gradients between weathered, carbonate-rich serpentinite breccia and serpentinite. Mixing of oxidized seawater and strongly reducing hydrothermal fluid at moderate temperatures created conditions capable of supporting microbial activity. Dense microbial colonies are fossilized in brucite−calcite veins that are strongly enriched in organic carbon (up to 0.5 wt.% of the total carbon) but depleted in 13 C (δ 13 C TOC = −19.4‰). We detected a combination of bacterial diether lipid biomarkers, archaeol, and archaeal tetraethers analogous to those found in carbonate chimneys at the active Lost City hydrothermal field. The exposure of mantle rocks to seawater during the breakup of Pangaea fueled chemolithoautotrophic microbial communities at the Iberia Margin, possibly before the onset of seafloor spreading. Lost City-type serpentinization systems have been discovered at midocean ridges, in forearc settings of subduction zones, and at continental margins. It appears that, wherever they occur, they can support microbial life, even in deep subseafloor environments.serpentinization | microfossils | lipid biomarkers | brucite−calcite | passive margin

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The influence of temperature and seawater carbonate saturation state on <sup>13</sup>C-<sup>18</sup>O bond ordering in bivalve mollusks

Cited by 44 publications

References 62 publications

Pronounced zonal heterogeneity in Eocene southern high-latitude sea surface temperatures

Pronounced zonal heterogeneity in Eocene southern high-latitude sea surface temperatures

Theoretical constraints on the effects of pH, salinity, and temperature on clumped isotope signatures of dissolved inorganic carbon species and precipitating carbonate minerals

Fluid mixing and the deep biosphere of a fossil Lost City-type hydrothermal system at the Iberia Margin

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