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在中国成都复杂大气中进行的 OH 自由基测量的比较。

Intercomparison of OH radical measurement in a complex atmosphere in Chengdu, China.

机构信息

Key Laboratory of Environment Optics and Technology, Anhui Institute of Optics and Fine Mechanics, HFIPS, Chinese Academy of Sciences, Hefei, China; University of Science and Technology of China, Hefei, China.

Key Laboratory of Environment Optics and Technology, Anhui Institute of Optics and Fine Mechanics, HFIPS, Chinese Academy of Sciences, Hefei, China.

出版信息

Sci Total Environ. 2022 Sep 10;838(Pt 1):155924. doi: 10.1016/j.scitotenv.2022.155924. Epub 2022 May 14.

Abstract

Atmospheric oxidation is a driving force of complex air pollution, and accurate hydroxyl radical (OH) measurement is helpful in investigating the radical-cored photooxidation mechanism in the troposphere. A self-developed laser-induced fluorescence instrument by the Anhui Institute of Optics Fine Mechanics, Chinese Academy of Sciences (AIOFM-LIF), was able to measure OH concentration with high sensitivity and good time resolution, and a detection limit of 1.7 × 10 cm (1σ, 30 s). A long-period, multi-level intercomparison of hydroxyl radical (OH) measurements between AIOFM-LIF and PKU-LIF (the Peking University laser-induced fluorescence system) was conducted in Chengdu, China. The measurement between two instruments was in excellent agreement in the 5-min time resolution. Linear regression analysis reported a linear slope of 0.96 with a 0.68 × 10 cm offset, and the correlation coefficient R was 0.85. The overall linearity with only a slight offset indicated a negligible influence on OH measurement. No noticeable artifacts from ozonolysis were observed under the condition of high ozone and ozonolysis-related compound concentrations. In addition to the subtraction of background signal through wavelength modulation, the dynamic correction on ozone photolysis interference ensured high intercomparison quality in both relatively constant and rapidly varying periods. Based on the reliability of OH and OH, comparisons under different oxidation-related species (NOx, VOCs, O, PM) levels and typical scenarios (rich-BVOC and high-reactivity) were carried out to evaluate the performance under complex atmospheres. A slightly higher drift was observed in a certain scenario, but the general data variability due to environmental changes did not affect the measurement accuracy. The intercomparison demonstrated that both systems are able to achieve reliable OH data under typical conditions of complex atmospheric pollution in China. Additional improvements are necessary for future intercomparisons in order to enhance the confidence in OH detection accuracy.

摘要

大气氧化是复杂空气污染的驱动力,准确测量羟基自由基(OH)有助于研究对流层中自由基核心光氧化机制。中国科学院安徽光学精密机械研究所(AIOFM)自主研发的激光诱导荧光仪(AIOFM-LIF)能够以高灵敏度和良好的时间分辨率测量 OH 浓度,检测限为 1.7×10^6cm^-1(1σ,30s)。在中国成都,AIOFM-LIF 和 PKU-LIF(北京大学激光诱导荧光系统)之间进行了长时间、多层次的羟基自由基(OH)测量相互比对。两种仪器在 5min 时间分辨率下的测量结果非常吻合。线性回归分析报告了 0.96 的线性斜率和 0.68×10^6cm^-1 的偏移量,相关系数 R 为 0.85。整体线性关系仅略有偏移,表明对 OH 测量的影响可以忽略不计。在高臭氧和与臭氧分解相关的化合物浓度条件下,未观察到臭氧分解产生的明显人为产物。除了通过波长调制减去背景信号外,臭氧光解干扰的动态校正还确保了在相对恒定和快速变化的时间段内具有较高的相互比较质量。基于 OH 和 OH 的可靠性,在不同氧化相关物种(NOx、VOCs、O、PM)水平和典型场景(富-BVOC 和高反应性)下进行了比较,以评估在复杂大气条件下的性能。在某些场景下观察到略微较高的漂移,但由于环境变化引起的一般数据可变性不会影响测量精度。相互比较表明,在典型的中国复杂大气污染条件下,两个系统都能够获得可靠的 OH 数据。为了提高 OH 检测精度的可信度,未来的相互比较还需要进一步改进。

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