Peroxy radicals as measured in ROSE and estimated from photostationary state deviations
Peroxy radicals as measured in ROSE and estimated from photostationary state deviations
复制标题
在 ROSE 中测量的过氧自由基以及根据光稳态偏差估算的过氧自由基
DOI：
10.1029/93jd01794
复制
发表时间：
1993
影响因子：
--
通讯作者：
R. Martin
中科院分区：
文献类型：
--
作者：
C. Cantrell;R. Shetter;J. Calvert;D. Parrish;F. Fehsenfeld;P. Goldan;W. Kuster;E. Williams;H. Westberg;G. Allwine;R. Martin
使用化学放大仪（CA）对过氧自由基浓度进行了环境测量，并通过光稳态偏差（PSSD）独立确定，该偏差源于对臭氧（O₃）、一氧化氮（NO）、二氧化氮（NO₂）和jNO₂的同时测量，其反应式为NO₂ + hv (+O₂) ⇌ NO + O₃。这些数据是在1990年7月的19天里，于南方环境中的农村氧化剂实验中收集的。在很多天里，观察到这两种方法之间有相当好的一致性，尽管在某些天里，PSSD方法的估计值要高出多达2倍。估计值之间出现的差异可能源于几个方面：RO₂ - HO₂仪器校准的不确定性、臭氧背景的快速变化、间歇性云层覆盖导致的太阳通量的快速改变，以及PSSD方法所需的对[NO]、[NO₂]、[O₃]和jNO₂同时测量的不精确性。讨论了两种测量技术中偏差的可能来源。利用两天测量的一系列痕量气体浓度进行了过氧自由基浓度的理论估计，其中一天（7月14日）CA和PSSD对过氧自由基浓度的估计值差异显著，另一天（7月11日）两者显示出良好的一致性。7月11日的理论估计值与两种方法的结果吻合良好。7月14日的理论估计值介于CA和PSSD估计值之间。这些结果表明，PSSD方法在某些天可能倾向于高估，并且/或者CA方法由于所讨论的原因可能倾向于低估。
Ambient measurements of peroxy radical concentrations were made using the chemical amplifier (CA) and determined independently from photostationary state deviations (PSSD), NO2 + hv (+O2) ⇌ NO + O3, derived from simultaneous measurements of O3, NO, NO2 and jNO2. The data were collected in the Rural Oxidants in the Southern Environment experiment during 19 days of July 1990. A reasonably good correspondence between the two methods is observed for many of the days, although estimates from the PSSD method for some of the days are higher by as much as a factor of 2. Scatter observed between estimates probably results from several sources: uncertainties in the calibration of the RO2-HO2 instrument, rapid changes in the ozone background, rapid alterations in the solar flux induced by intermittent cloud cover, and imprecisions in making simultaneous measurements of [NO], [NO2], [O3], and jNO2 required for the PSSD method. Possible origins of bias in the two measurement techniques are discussed. Theoretical estimates of the peroxy radical concentrations were made using the measured suite of trace gas concentrations for 2 days, one for which the CA and PSSD estimates of peroxy radical concentrations differed significantly (July 14) and one for which they showed good agreement (July 11). Theoretical estimates for July 11 checked well with the results from both methods. Those for July 14 fell between the GA and PSSD estimates. These results suggest that the PSSD method may have a bias toward higher estimates on some days and/or that the CA method may have a bias for the lower estimates for reasons which are discussed.