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应用生态学报 ›› 2019, Vol. 30 ›› Issue (6): 1847-1853.doi: 10.13287/j.1001-9332.201906.011

• 稳定同位素生态学专栏 • 上一篇    下一篇

利用次溴酸盐氧化结合盐酸羟胺还原法测定大气气溶胶样品铵态氮同位素

项妍琨1,2, 曹芳1,2,*, 杨笑影1,2, 翟晓瑶1,2, 章炎麟1,2   

  1. 1南京信息工程大学气候与环境变化国际合作联合实验室大气环境中心, 南京 210044;
    2南京信息工程大学气象灾害预报预警与评估协同创新中心/气象灾害教育部重点实验室, 南京 210044
  • 收稿日期:2018-11-19 出版日期:2019-06-15 发布日期:2019-06-15
  • 通讯作者: * E-mail: caofangle@163.com
  • 作者简介:项妍琨,女,1994年生,硕士研究生.主要从事大气气溶胶化学研究. E-mail: xyk6688@126.com
  • 基金资助:
    国家重点研发计划项目(2017YFC0212302)、国家自然科学基金项目(91644103)和江苏省自然科学基金项目(BK20180040)资助

Hypobromite oxidation combined with hydroxylamine hydrochloride reduction method for analyzing ammonium nitrogen isotope in atmospheric samples.

XIANG Yan-kun1,2, CAO Fang1,2,*, YANG Xiao-ying1,2, ZHAI Xiao-yao1,2, ZHANG Yan-lin1,2   

  1. 1Yale-NUIST Center on Atmospheric Environment, International Joint Laboratory on Climate and Environment Change (ILCEC), Nanjing University of Information Science & Technology, Nanjing 210044, China;
    2Collaborative Innovation Center on Forecast and Evaluation of Meteorological Disasters (CIC-FEMD), Nanjing University of Information Science & Technology/Key Laboratory of Meteorological Disaster, Ministry of Education (KLME), Nanjing 210044, China
  • Received:2018-11-19 Online:2019-06-15 Published:2019-06-15
  • Supported by:
    This work was supported by the National Key Research and Development Program of China (2017YFC0212302), the National Natural Science Foundation of China (91644103), and the Natural Science Foundation of Jiangsu Province (BK20180040)

摘要: 硝酸铵、硫酸铵和硫酸氢铵等铵盐作为PM2.5中主要的二次无机气溶胶污染物,在灰霾形成过程中发挥了重要作用.关于其来源及转化过程的研究备受关注.本文在前人研究基础上,基于稳定同位素分析技术改进了样品进样量,增加了调节浸提液pH的步骤,给出了一种能够快速、准确测量大气样品中铵态氮同位素的化学转化方法.即向含有0.25 μg·mL-1铵态氮的4 mL大气气溶胶滤膜样品浸提液中加入碱性次溴酸盐溶液,使铵盐(NH4+)氧化为亚硝酸盐(NO2-);然后通过调节pH值,在 pH<0.3 的条件下,使用盐酸羟胺将亚硝酸盐(NO2-)还原为氧化亚氮气体(N2O),最终通过Precon-GasBench-IRMS系统的连用实现大气气溶胶样品中的铵态氮同位素的测定.该方法所需进样含量低,避免了剧毒易制爆试剂的使用,重复测试精确度可达到0.2‰(n=10).通过调节大气气溶胶滤膜样品浸提液的pH可提高还原效率(约100%).测量精确度和准确度满足了大气气溶胶中颗粒态铵的测定,有助于进一步开展大气铵盐的来源、化学转化过程、传输沉降等研究.

Abstract: Ammonium salts, including ammonium nitrate, ammonium sulfate and ammonium hydrogen sulfate, are the main components of secondary inorganic aerosols and play an important role in the formation of haze events. The sources and transformation processes of atmospheric ammonium have received more and more attention. In this study, we modified the previous stable isotope analysis technique by improving the injection volume and adding a pH adjustment step, which gave a rapid and accurate measurement of ammonium nitrogen isotope ratio in atmospheric aerosol samples. Firstly, we added alkaline hypobromite to the extracted solution of the atmospheric aerosol filter samples (0.25 μg·mL-1 ammonium nitrogen in 4 mL) to oxidize ammonium (NH4+) to nitrite (NO2-). Then, after adjusting the pH, nitrite (NO2-) was reduced to nitrous oxide (N2O) by hydroxylamine hydrochloride under pH <0.3. Finally, nitrous oxide (N2O) was analyzed by Precon-GasBench-IRMS system to measure ammonium nitrogen isotope ratio. Our approach required low amount of NH4+ and avoided the use of highly toxic and explosive reagents. Meanwhile, the precision of our method could reach as high as 0.2‰ (n=10). This method could increase the NH4+ reduction efficiency to 100% at a condition of pH <0.3 and satisfy the demands of precision and accuracy for determination of ammonium nitrogen isotope in atmospheric aerosol samples. This method would help us better understand the sources, evolutions, chemical and deposition processes of atmospheric ammonium.