Clumped Isotope Analysis of Calcite and Dolomite Mixtures Using Selective Acid Extraction

Acid extraction methods have been used in the last half century to selectively extract the CO_(2)produced from different carbonate minerals in mixed samples.However,these methods are often time-consuming and labor intensive.Their application to clumped isotope(Δ47)analysis has not been demonstrated.We propose here an acid extraction method with phosphoric acid for bulk stable and clumped isotope analysis that treats mixtures of calcite and dolomite the same regardless of the proportional composition.CO_(2)evolved from calcite is extracted by allowing a reaction with phosphoric acid to proceed for 10 min at 50℃.We then extract CO_(2)evolved from dolomite by rapid ramping the acid temperature from 50 to 90℃and allowing the reaction to complete.The experimental results show that our method yields accurate calcite and dolomiteΔ_(47)values from mixed samples under different proportional compositions.Our method also displays equal or higher accuracy for calciteδ^(13)C and dolomiteδ^(13)C andδ^(18)O values from mixtures when compared to previous studies.Our approach exhibits higher sample throughput than previous methods,is adequate for clumped isotopic analysis and simplifies the reaction progression from over 24 h to less than 2 h,while maintaining relatively high isotopic obtaining accuracy.It yet poorly resolves calciteδ18O values,as found with previous methods.

Clumped isotope analysis of lacustrine endogenic carbonates and implications for paleo-temperature reconstruction:A case study from Dali Lake

Carbonate clumped isotope(Δ47)is a new and reliable geothermometer.Endogenic carbonates in lake sediments are good archives to reconstruct lake water temperature using clumped isotope thermometry.However,applications of carbonate clumped isotope thermometry to lacustrine carbonates are still scarce because the existed organic and/or sulfur contaminants in such samples interfere with clumped isotope analysis and cause notable temperature biases.Therefore,exploring an effective way to remove contamination is a prerequisite to widely applying carbonate clumped isotope thermometry to lake sediments.By pretreating fine-grained endogenic carbonates from Dali lake sediments with hydrogen peroxide of different concentrations for different lengths of time,we conducted a series of conditional experiments to seek the optimal pretreatment condition for clumped isotope analysis.Δ47,Δ48 offset and 49 parameter were obtained from clumped isotope measurements to assess the effect of contamination removal.Results showed that untreated samples("0%-0")had a very high 49 parameter.After the treatment with hydrogen peroxide,the 49 parameter was significantly reduced while theΔ48 offset evidently increased.TheΔ47,Δ48 offset and 49 parameter of samples pretreated under different conditions showed significant variability,even though the measuredΔ47 temperatures changed within a relatively narrow range(i.e.,from 17.0±1.3 to 22.8±1.6°C).Among various treated samples,the sample"3%-8"yielded a smallerΔ48 offset and 49 parameter,and lowerΔ47 temperature of 17.0±1.3°C.Therefore,"reacting with 3%hydrogen peroxide for 8 h"was suggested to be the optimal condition for removing contaminants from lacustrine endogenic carbonates prior to clumped isotope analysis.At the time when the pretreatment condition was too intense(i.e.,H2O2 concentration>3%and/or reaction time>8 h),secondary contaminants might have been generated in the closed reaction system,whose ultimately transformed state may interfere with masses 47,48.Using the optimal pretreatment procedure,we obtained reasonableΔ47 temperature changes during the last deglaciation and found a temperature decrease of about 6°C in Northern China during the Younger Dryas period.Our study demonstrates a great potential of applying carbonate clumped isotope thermometry to lacustrine carbonates for paleo-temperature and paleo-elevation reconstructions in the future.

The dating and temperature measurement technologies for carbonate minerals and their application in hydrocarbon accumulation research in the paleouplift in central Sichuan Basin, SW China

A new method for reconstructing the geological history of hydrocarbon accumulation is developed, which are constrained by U-Pb isotope age and clumped isotope((35)47) temperature of host minerals of hydrocarbon-bearing inclusions. For constraining the time and depth of hydrocarbon accumulation by the laser in-situ U-Pb isotope age and clumped isotope temperature, there are two key steps:(1) Investigating feature, abundance and distribution patterns of liquid and gaseous hydrocarbon inclusions with optical microscopes.(2) Dating laser in-situ U-Pb isotope age and measuring clumped isotope temperature of the host minerals of hydrocarbon inclusions. These technologies have been applied for studying the stages of hydrocarbon accumulation in the Sinian Dengying gas reservoir in the paleo-uplift of the central Sichuan Basin. By dating the U-Pb isotope age and measuring the temperature of clumped isotope((35)47) of the host minerals of hydrocarbon inclusions in dolomite, three stages of hydrocarbon accumulation were identified:(1) Late Silurian: the first stage of oil accumulation at(416±23) Ma.(2) Late Permian to Early Triassic: the second stage of oil accumulation between(248±27) Ma and(246.3±1.5) Ma.(3) Yanshan to Himalayan period: gas accumulation between(115±69) Ma and(41±10) Ma. The reconstructed hydrocarbon accumulation history of the Dengying gas reservoir in the paleo-uplift of the central Sichuan Basin is highly consistent with the tectonic-burial history, basin thermal history and hydrocarbon generation history, indicating that the new method is a reliable way for reconstructing the hydrocarbon accumulation history.