Effects of pyrolysis temperature on the photooxidation of water-soluble fraction of wheat straw biochar based on 21 ​T FT-ICR mass spectrometry

Amy M. McKenna , Martha L. Chacón-Patiño , Holly K. Roth , William Bahureksa , Robert B. Young , James A. Ippolito , Yan Xin , Thomas Borch , Antony J. Williams , Huan Chen
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Abstract

Biochar, formed through the pyrolysis or burning of organic wastes, has a complex chemical composition influenced by feedstock, pyrolysis temperature, and reaction conditions. Water-soluble, dissolved black carbon species released from biochar comprise one of the most photoreactive organic matter fractions. Photodegradation of these water-soluble species from wheat straw biochar, produced at different pyrolysis temperatures in laboratory microcosms, resulted in noticeable compositional differences. This study characterized water-soluble transformation products formed through the photodegradation of wheat straw biochar pyrolyzed at 300, 400, 500, or 600°C by electrospray ionization 21 ​T Fourier transform ion cyclotron resonance mass spectrometry (21T FT-ICR MS). We also evaluated global trends in the toxicity of these water-soluble fractions using MicroTox™ to assess the impacts of pyrolysis temperature. Additionally, we examined biochar surface morphology after photodegradation and observed minimal change after irradiation for 48 ​h, though the total yield of water-soluble biochar species varied with pyrolysis temperature. Trends in toxicity observed from MicroTox® analysis reveal that water-soluble photoproducts from biochar produced at 300°C and 900°C are nearly three times as toxic compared to dark controls. The ultrahigh resolving power of 21T FT-ICR MS allows for the separation of tens of thousands of highly oxidized, low-molecular-weight (<1 ​kDa) species, showing that photoproducts span a wider range of H/C and O/C ratios compared to their dark analogs. This study highlights the impacts of photodegradation on the molecular composition of water-soluble biochar species and underscores the influence of pyrolysis temperature on the quantity and composition of dissolved organic species.

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基于 21 T FT-ICR 质谱法的热解温度对小麦秸秆生物炭水溶部分光氧化作用的影响
生物炭是通过热解或焚烧有机废物形成的,其化学成分复杂,受原料、热解温度和反应条件的影响。生物炭中释放出的水溶性溶解黑碳是光活性最强的有机物部分之一。小麦秸秆生物炭中的这些水溶性物质在实验室微生态系统中以不同的热解温度产生,其光降解导致了明显的成分差异。本研究通过电喷雾离子化 21T 傅立叶变换离子回旋共振质谱法(21T FT-ICR MS)对在 300、400、500 或 600°C 高温下热解的小麦秸秆生物炭光降解形成的水溶性转化产物进行了鉴定。我们还使用 MicroTox™ 评估了这些水溶性馏分毒性的全球趋势,以评估热解温度的影响。此外,我们还检查了光降解后的生物炭表面形态,观察到辐照 48 小时后生物炭表面形态变化极小,但水溶性生物炭的总产量随热解温度的变化而变化。从 MicroTox® 分析中观察到的毒性趋势表明,在 300°C 和 900°C 温度下生产的生物炭产生的水溶性光产物的毒性几乎是黑暗对照组的三倍。21T FT-ICR MS 的超高分辨能力可分离数以万计的高度氧化、低分子量(1 kDa)物种,表明与黑暗类似物相比,光产物的 H/C 和 O/C 比率范围更广。这项研究强调了光降解对水溶性生物炭分子组成的影响,并强调了热解温度对溶解有机物数量和组成的影响。
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