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Abstract
Abstract. Laser-induced fluorescence (LIF) is a widely used technique for both laboratory-based and ambient atmospheric chemistry measurements. However, LIF instruments require calibrations in order to translate instrument response into concentrations of chemical species. Calibration of LIF instruments measuring OH and HO2 (HOx) typically involves the photolysis of water vapor by 184.9 nm light, thereby producing quantitative amounts of OH and HO2. For ground-based HOx instruments, this method of calibration is done at one pressure (typically ambient pressure) at the instrument inlet. However, airborne HOx instruments can experience varying cell pressures, internal residence times, temperatures, and humidity during flight. Therefore, replication of such variances when calibrating in the lab is essential to acquire the appropriate sensitivities. This requirement resulted in the development of the APACHE (All Pressure Altitude-based Calibrator for HOx Experimentation) chamber to characterize the sensitivity of the airborne LIF-FAGE (fluorescence assay by gas expansion) HOx instrument, HORUS, which took part in an intensive airborne campaign, OMO-Asia 2015. It utilizes photolysis of water vapor but has the additional ability to alter the pressure at the nozzle of the HORUS instrument. With APACHE, the HORUS instrument sensitivity towards OH (26.1–7.8 cts s−1 pptv−1 mW−1, ±22.6 % 1σ; cts stands for counts by the detector) and HO2 (21.2–8.1 cts s−1 pptv−1 mW−1, ±22.1 % 1σ) was characterized to the external pressure range at the instrument nozzle of 227–900 mbar. Measurements supported by a computational fluid dynamics model, COMSOL Multiphysics, revealed that, for all pressures explored in this study, APACHE is capable of initializing a homogenous flow and maintaining near-uniform flow speeds across the internal cross section of the chamber. This reduces the uncertainty regarding average exposure times across the mercury (Hg) UV ring lamp. Two different actinometrical approaches characterized the APACHE UV ring lamp flux as 6.37×1014(±1.3×1014) photons cm−2 s−1. One approach used the HORUS instrument as a transfer standard in conjunction with a calibrated on-ground calibration system traceable to NIST standards, which characterized the UV ring lamp flux to be 6.9(±1.1)×1014 photons cm−2 s−1. The second approach involved measuring ozone production by the UV ring lamp using an ANSYCO O3 41 M ozone monitor, which characterized the UV ring lamp flux to be 6.11(±0.8)×1014 photons cm−2 s−1. Data presented in this study are the first direct calibrations of an airborne HOx instrument, performed in a controlled environment in the lab using APACHE.
Highlights
It is well known that the hydroxyl (OH) radical is a potent oxidizing agent in daytime photochemical degradation of pollutants sourced from anthropogenic and biogenic processes, accelerating their removal from our atmosphere
Airborne HOx instruments can experience varying cell pressures, internal residence times, temperatures, and humidity during flight. Replication of such variances when calibrating in the lab is essential to acquire the appropriate sensitivities. This requirement resulted in the development of the APACHE (All Pressure Altitude-based Calibrator for HOx Experimentation) chamber to characterize the sensitivity of the airborne LIFFAGE HOx instrument, HORUS, which took part in an intensive airborne campaign, OMO-Asia 2015
Measurements supported by a computational fluid dynamics model, COMSOL Multiphysics, revealed that, for all pressures explored in this study, APACHE is capable of initializing a homogenous flow and maintaining near-uniform flow speeds across the internal cross section of the chamber
Summary
It is well known that the hydroxyl (OH) radical is a potent oxidizing agent in daytime photochemical degradation of pollutants sourced from anthropogenic and biogenic processes, accelerating their removal from our atmosphere. D. Marno et al.: Pressure-dependent calibration of LIF-FAGE using APACHE droperoxyl radical (HO2) plays a central role in atmospheric oxidation as it acts as a reservoir for OH but is involved in formation of other oxidants such as peroxides and impacts the cycling of pollutants such as NOx (=NO + NO2) (Lelieveld et al, 2002). Low atmospheric concentrations of HOx (Schlosser et al, 2009) and potential interferences (Faloona et al, 2004; Fuchs et al, 2011, 2016; Mao et al, 2012; Hens et al, 2014; Novelli et al, 2014) can make HOx measurements especially challenging. It is critical to utilize a calibration system that can suitably reproduce in-flight conditions to determine the instrument response to known levels of OH and HO2 to acquire robust HOx measurements
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