Tracking Photo-Oxidation Reactions of Aquatic Organic Matter Using Triple Oxygen Isotopes

IF 2.9 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

ACS Earth and Space Chemistry Pub Date : 2025-06-24 DOI:10.1021/acsearthspacechem.5c00057

Daniel R. Crocker*, Kevin M. Sutherland, Benjamin Freudenberg, Kimberly Alonso, Ann Pearson, Collin P. Ward and David T. Johnston*,

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Abstract

The three-isotope system of oxygen (¹⁶O, ¹⁷O, ¹⁸O) is a powerful tool to study environmental oxidation chemistry and cycling of oxygen-bearing species (e.g., sulfates, nitrates, carbonates, etc.). Despite its evident utility, little work has focused on extending the triple oxygen isotope (Δ’¹⁷O) tool to oxygen contained in organic matter (OM). This is largely due to methodological challenges with isolating OM-bound oxygen and preparing it for isotopic analysis. Herein, we report on a newly developed method for high-precision Δ’¹⁷O measurements of OM (Δ’¹⁷O precision of 0.020‰) and apply this technique to investigate partial photochemical oxidation of Suwannee River natural OM in air-equilibrated aquatic samples. Through this, we reveal that the oxygen isotope evolution of the Suwannee OM supports a model whereby OM partial photo-oxidation proceeds via one or more reactive oxygen intermediates. Our measurements further highlight the potential of triple oxygen isotope analyses on OM-bound oxygen to fingerprint OM oxidation pathways, redox chemistry, and source and synthesis reactions.

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利用三氧同位素跟踪水生有机物的光氧化反应

氧的三同位素体系（16O、17O、18O）是研究环境氧化化学和含氧物质（如硫酸盐、硝酸盐、碳酸盐等）循环的有力工具。尽管具有明显的实用性，但将三氧同位素（Δ ' 17O）工具扩展到有机物（OM）中所含氧的工作很少。这在很大程度上是由于分离om结合氧并准备其用于同位素分析的方法上的挑战。本文报道了一种新开发的高精度Δ ‘ 17O测量方法（Δ ’ 17O精度为0.020‰），并应用该技术研究了空气平衡水样品中Suwannee河天然OM的部分光化学氧化。通过这一研究，我们发现Suwannee OM的氧同位素演化支持一种模式，即OM通过一种或多种活性氧中间体进行部分光氧化。我们的测量结果进一步强调了OM结合氧的三氧同位素分析在OM氧化途径、氧化还原化学以及来源和合成反应方面的潜力。

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来源期刊

ACS Earth and Space Chemistry Earth and Planetary Sciences-Geochemistry and Petrology

CiteScore

5.30

自引率

11.80%

发文量

249

期刊介绍： The scope of ACS Earth and Space Chemistry includes the application of analytical, experimental and theoretical chemistry to investigate research questions relevant to the Earth and Space. The journal encompasses the highly interdisciplinary nature of research in this area, while emphasizing chemistry and chemical research tools as the unifying theme. The journal publishes broadly in the domains of high- and low-temperature geochemistry, atmospheric chemistry, marine chemistry, planetary chemistry, astrochemistry, and analytical geochemistry. ACS Earth and Space Chemistry publishes Articles, Letters, Reviews, and Features to provide flexible formats to readily communicate all aspects of research in these fields.