Tyler B. Coplen
Juske Horita
Sang-Tae Kim
2015
<p id="sp0005">Carbonate minerals provide a rich source of geochemical information because their <i>δ</i><sup>13</sup>C and <i>δ</i><sup>18</sup>O values provide information about surface and subsurface Earth processes. However, a significant problem is that the same <i>δ</i><sup>18</sup>O value is not reported for the identical carbonate sample when analyzed in different isotope laboratories in spite of the fact that the International Union of Pure and Applied Chemistry (IUPAC) has provided reporting guidelines for two decades. This issue arises because (1) the <i>δ</i><sup>18</sup>O measurements are performed on CO<sub>2</sub> evolved by reaction of carbonates with phosphoric acid, (2) the acid-liberated CO<sub>2</sub> is isotopically fractionated (enriched in <sup>18</sup>O) because it contains only two-thirds of the oxygen from the solid carbonate, (3) this oxygen isotopic fractionation factor is a function of mineralogy, temperature, concentration of the phosphoric acid, and <i>δ</i><sup>18</sup>O value of water in the phosphoric acid, (4) researchers may use any one of an assortment of oxygen isotopic fractionation factors that have been published for various minerals at various reaction temperatures, and (5) it sometimes is not clear how one should calculate <i>δ</i><sup>18</sup>O<sub>VPDB</sub> values on a scale normalized such that the <i>δ</i><sup>18</sup>O value of SLAP reference water is −55.5 ‰ relative to VSMOW reference water.</p>
<p id="sp0010">To enable researchers worldwide to publish the same <i>δ</i><sup>18</sup>O value (within experimental uncertainty) for the same carbonate sample, we have re-evaluated reported acid fractionation factors for calcite at 25, 50, and 75 °C and propose a revised relation for the temperature dependence of oxygen isotopic acid fractionation factor, <span id="mmlsi1" class="mathmlsrc"><span class="formulatext stixSupport mathImg" title="Click to view the MathML source" data-mathurl="/science?_ob=MathURL&_method=retrieve&_eid=1-s2.0-S0016703715000940&_mathId=si1.gif&_user=111111111&_pii=S0016703715000940&_rdoc=1&_issn=00167037&md5=28b351c4a3364b91eef66f01686e710c"><sub>α</sub>CO<sub>2</sub><sub>(</sub>ACID<sub>)</sub>-calcite</span><span class="mathContainer hidden"><span class="mathCode">αCO2(ACID)-calcite</span></span></span>, of</p>
<div id="e0005" class="formula">
<div class="mathml"><span class="mathmlsrc"><span class="mathmlsrc"><span class="formulatext stixSupport mathImg" title="Click to view the MathML source" data-mathurl="/science?_ob=MathURL&_method=retrieve&_eid=1-s2.0-S0016703715000940&_mathId=si2.gif&_user=111111111&_pii=S0016703715000940&_rdoc=1&_issn=00167037&md5=41e78095788c282f1d19094fba748d4b">1000ln<sub>α</sub>CO<sub>2</sub><sub>(</sub>ACID<sub>)</sub>-calcite=3.48(10<sup>3</sup>/T)-1.47</span><span class="mathContainer hidden"><span class="mathCode">1000lnαCO2(ACID)-calcite=3.48(103/T)-1.47</span></span></span></span>
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<p id="sp0015">where <i>T</i> is temperature in kelvin. At 25 °C, <span id="mmlsi3" class="mathmlsrc"><span class="formulatext stixSupport mathImg" title="Click to view the MathML source" data-mathurl="/science?_ob=MathURL&_method=retrieve&_eid=1-s2.0-S0016703715000940&_mathId=si3.gif&_user=111111111&_pii=S0016703715000940&_rdoc=1&_issn=00167037&md5=4ed80d0dbcfcc5bd9e919d5d2bbd40c1"><sub>α</sub>CO<sub>2</sub><sub>(</sub>ACID<sub>)</sub>-calcite=1.01025</span><span class="mathContainer hidden"><span class="mathCode">αCO2(ACID)-calcite=1.01025</span></span></span>, the most commonly accepted value for this quantity. We propose a normalization protocol in which (1) the internationally distributed carbonate isotopic reference materials NBS 18 and NBS 19 are interspersed among carbonate samples analyzed by treatment with phosphoric acid, (2) the <i>δ</i><sup>18</sup>O values of the calcite reference materials and the carbonate samples are calculated, respectively, by using the <span id="mmlsi4" class="mathmlsrc"><span class="formulatext stixSupport mathImg" title="Click to view the MathML source" data-mathurl="/science?_ob=MathURL&_method=retrieve&_eid=1-s2.0-S0016703715000940&_mathId=si4.gif&_user=111111111&_pii=S0016703715000940&_rdoc=1&_issn=00167037&md5=9f65c84ff2f44959b66e08525b62895a"><sub>α</sub>CO<sub>2</sub><sub>(</sub>ACID<sub>)</sub>-calcite</span><span class="mathContainer hidden"><span class="mathCode">αCO2(ACID)-calcite</span></span></span> relation above and oxygen-isotope acid fractionation factors appropriate for the sample mineralogy and reaction temperature, (3) the <i>δ</i><sup>18</sup>O values of solid carbonate samples are determined on the VPDB scale (<i>δ</i><sup>18</sup>O<sub>VPDB</sub>) with IUPAC-recommended scale expansion such that the <i>δ</i><sup>18</sup>O of SLAP reference water is −55.5 ‰ relative to VSMOW reference water by normalizing <i>δ</i><sup>18</sup>O values of carbonate samples with 2014-IUPAC-recommended <i>δ</i><sup>18</sup>O values of NBS 18 and NBS 19, and (4) <i>δ</i><sup>18</sup>O values on the VPDB scale are converted to <i>δ</i><sup>18</sup>O values on the VSMOW-SLAP scale by using IUPAC recommendations.</p>
<p id="sp0020">To ease calculations in the protocol, a software application titled “Carbon and Oxygen Isotopic Normalization Tool for Carbonates” is available that relies upon IUPAC-recommended <i>δ</i><sup>13</sup>C and <i>δ</i><sup>18</sup>O values of carbonate isotopic reference materials</p>
<p>(<span id="ir0045" class="interref" data-locatortype="url" data-locatorkey="http://isotopes.usgs.gov/research/topics/carbonatesnormalizationtool.html"><a class="cExLink" href="http://isotopes.usgs.gov/research/topics/carbonatesnormalizationtool.html" target="externObjLink" data-itrprs="Y" data-url="/science/RedirectURL?_method=externObjLink&_locator=url&_cdi=271865&_issn=00167037&_origin=article&_zone=art_page&_targetURL=http%253A%252F%252Fisotopes.usgs.gov%252Fresearch%252Ftopics%252Fcarbonatesnormalizationtool.html">http://isotopes.usgs.gov/research/topics/carbonatesnormalizationtool.html</a></span>).</p>
application/pdf
10.1016/j.gca.2015.02.011
en
Elsevier
Normalization of stable isotope data for carbonate minerals: implementation of IUPAC guideline
article