Cui Linlin, Wang Xu, Feng Lianjun, Zhang Xiaomei
State Key Laboratory of Lithospheric and Environmental Coevolution, Institute of Geology and Geophysics, Chinese Academy of Sciences, Beijing, China.
Beijing City Shunyi District Testing Center for Metrology, Food and Drugs, Beijing, China.
Rapid Commun Mass Spectrom. 2025 Nov 15;39(21):e10108. doi: 10.1002/rcm.10108.
The conventional method for measuring carbon and oxygen isotopes in carbonates involves the reaction of carbonate minerals with phosphoric acid (PPA) to generate CO, followed by purification and isotopic analysis. During this reaction, a temperature-dependent oxygen isotope acid fractionation factor (AFF) is introduced, as not all oxygen is released in CO. Although the temperature dependence of AFF has been extensively studied in pure carbonate minerals, little research has been conducted on AFF variations in mixed carbonate minerals with diverse chemical and mineralogical compositions. This study aims to investigate the range of AFF variations in carbonates containing multiple mineral phases.
Oxygen isotope compositions of CO produced from CaCO-MgCO mixed minerals reacting with PPA at 25°C, 50°C, 70°C, and 90°C were analyzed using a GasBench II system coupled with a Thermo Finnigan Delta V Plus isotope ratio mass spectrometer.
The AFF values for CaCO-MgCO mixed minerals fall between those of pure calcite and dolomite, generally aligning with theoretical predictions. Additionally, the fractionation gradient (dδO/dT) increases with rising mole Mg and dolomite content, indicating a systematic trend in fractionation behavior.
These findings provide a framework for AFF correction based on mole Mg or dolomite content, enhancing the reliability and precision of oxygen isotope measurements in natural impure carbonates.
测量碳酸盐中碳和氧同位素的传统方法是使碳酸盐矿物与磷酸(PPA)反应生成CO,然后进行纯化和同位素分析。在这个反应过程中,会引入一个与温度相关的氧同位素酸分馏因子(AFF),因为并非所有的氧都以CO的形式释放出来。尽管已经在纯碳酸盐矿物中对AFF的温度依赖性进行了广泛研究,但对于具有不同化学和矿物组成的混合碳酸盐矿物中AFF的变化研究较少。本研究旨在探究含有多个矿物相的碳酸盐中AFF变化的范围。
使用GasBench II系统与Thermo Finnigan Delta V Plus同位素比率质谱仪联用,分析CaCO-MgCO混合矿物在25°C、50°C、70°C和90°C下与PPA反应产生的CO的氧同位素组成。
CaCO-MgCO混合矿物的AFF值介于纯方解石和白云石之间,总体上与理论预测相符。此外,分馏梯度(dδO/dT)随着Mg摩尔含量和白云石含量的增加而增大,表明分馏行为存在系统趋势。
这些发现为基于Mg摩尔含量或白云石含量的AFF校正提供了一个框架,提高了天然不纯碳酸盐中氧同位素测量的可靠性和精度。