稳定同位素示踪海洋大气硝酸盐来源及形成机制

doi:10.11978/2024194

摘要/Abstract

摘要：

大气中的硝酸盐($\mathrm{NO}_{3}^{-}$)是氮氧化物(NO_x)通过与臭氧(O₃)、羟基自由基(·OH)等多种氧化剂反应生成的关键产物, 是大气中的主要污染物之一, 对空气质量、气候和生态系统等产生重要影响。本文综述了海洋大气中$\mathrm{NO}_{3}^{-}$的生成机制、氧化途径和氮氧同位素(如δ¹⁵N、δ¹⁸O)特征的全球分布, 探讨了不同氧化剂(如O₃和·OH)在$\mathrm{NO}_{3}^{-}$生成中的作用。其中, 碳氢化合物/二甲基硫(hydrocarbon/dimethyl sulfate, HC/DMS)途径、N₂O₅与含氯气(Cl₂)气溶胶的非均相反应以及NO₂与活性卤素化合物反应显著影响了海洋大气中$\mathrm{NO}_{3}^{-}$的生成机制并导致较高的δ¹⁸O值。结合全球观测数据, 发现不同海域和沿海城市$\mathrm{NO}_{3}^{-}$的δ¹⁵N和δ¹⁸O具有显著差异, 这可能反映了区域内的污染源、光化学条件及大气反应路径的差异。此外, $\mathrm{NO}_{3}^{-}$会通过大气沉降进入海洋, 对海洋氮循环产生影响。未来研究应加强对全球不同区域的长期监测和数据收集, 完善氧化过程贡献的定量评估, 从而能更系统地理解大气$\mathrm{NO}_{3}^{-}$的生成机制及其对海洋生态系统和气候变化的影响。

关键词: 稳定同位素, 硝酸盐, 海洋大气, 海洋大气硝酸盐沉降, 氮氧化物

Abstract:

Nitrate ($\mathrm{NO}_{3}^{-}$) in the atmosphere, a key product formed from nitrogen oxides (NO_x) through reactions with multiple oxidants such as ozone (O₃) and hydroxyl radicals (·OH), is one of the main atmospheric pollutants, impacting air quality, climate, and ecosystems. This paper reviews the formation mechanisms, oxidation pathways, and global distribution of nitrogen and oxygen isotopic (such as δ¹⁵N and δ¹⁸O) signatures in marine atmospheric $\mathrm{NO}_{3}^{-}$, focusing on the roles of various oxidants like O₃ and ·OH. Notably, the hydrocarbon/dimethyl sulfide (HC/DMS) pathway, the heterogeneous reaction of N₂O₅with chlorine-containing (Cl₂) aerosols, and the reaction of NO₂ with reactive halogen compounds significantly impact the formation mechanisms of $\mathrm{NO}_{3}^{-}$ in the marine atmosphere and result in elevated δ¹⁸O values. Based on global observational data, the δ¹⁵N and δ¹⁸O composition of $\mathrm{NO}_{3}^{-}$ shows significant variations across different oceanic regions and coastal cities, probably reflecting regional differences in pollution sources, photochemical conditions, and atmospheric reaction pathways. Additionally, $\mathrm{NO}_{3}^{-}$ deposition into marine systems affects the nitrogen cycle within the oceans. Future research should prioritize long-term monitoring and data collection across diverse global regions to enhance quantitative assessments of oxidant contributions, thereby providing a more systematic understanding of atmospheric $\mathrm{NO}_{3}^{-}$ formation mechanisms and their implications for marine ecosystems and climate change.

Key words: stable isotopes, nitrate, marine atmosphere, marine atmospheric nitrate deposition, NO_x

中图分类号:

P732

陈天舒, 肖红伟, 关文凯, 肖化云. 稳定同位素示踪海洋大气硝酸盐来源及形成机制[J]. 热带海洋学报, 2025, 44(3): 167-178.

CHEN Tianshu, XIAO Hongwei, GUAN Wenkai, XIAO Huayun. Tracing the sources and formation mechanisms of marine atmospheric nitrate using stable isotopes[J]. Journal of Tropical Oceanography, 2025, 44(3): 167-178.

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预处理方法	可测定同位素	优点	缺点	文献
蒸馏法	N	可应用于不同类型的样品, 不需要昂贵的设备; 适用低浓度样品	步骤较繁琐; 容易受到有机物和其他含氮化合物的干扰、容易发生同位素分馏, 导致精度和灵敏度有限	Diaconu et al, 2005
扩散法	N	所需设备和试剂相对简单和廉价; 可批量处理样品; 耗时较短	样品需求量较大; 耗时较长; 不适合低浓度样品的同位素分析; 不完全扩散可能引起同位素分馏, 导致较大的误差	Brooks, 1989; 孙文青等, 2019
热解法	N、O	避免了样品与反应管氧同位素的交换, 适用于微量样品的高精度同位素分析	设备昂贵, 对操作条件要求严格, 需要经验丰富的技术人员	Michalski et al, 2002
离子交换树脂法	N、O	具有高选择性, 能去除干扰离子; 适用于低浓度样品	需要的样品量较大, 耗时较长;交换和洗脱过程中可能会导致部分样品损失; 费用较高	Chang et al, 1999; Silva et al, 2000
细菌法	N、O	检出限较低; 前处理方法简单; 成本较低; 可以同时分析氮和氧同位素	需要细菌培养和较长的反应时间; 需要无氧条件操作, 易受氧气污染; 细菌的代谢特性可能影响同位素分析的结果, 导致结果不稳定	毛绪美等, 2005; 尹希杰等, 2023
化学法	N、O	反应速度快; 检出限低; 结果稳定	使用剧毒试剂; 试剂纯度和质量要求高, 需要精确控制反应条件(如温度、酸碱度)以确保结果准确	McIlvin et al, 2005; 张雯淇等, 2019