Development of an incoherent broadband cavity-enhanced absorption spectrometer for in situ measurements of HONO and NOsub2/sub

摘要

Gaseous nitrous acid (HONO) is an important source of OH radicals in the troposphere. However, its source, especially that during daytime hours remains unclear. We present an instrument for simultaneous unambiguous measurements of HONO and NOsub2/sub with high time resolution based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS). To achieve robust performance and system stability under different environment conditions, the current IBBCEAS instrument has been developed with significant improvements in terms of efficient sampling as well as resistance against vibration and temperature change, and the IBBCEAS instrument also has low power consumption and a compact design that can be easily deployed on different platforms powered by a high-capacity lithium ion battery. The effective cavity length of the IBBCEAS was determined using the absorption of Osub2/sub - Osub2/sub to account for the “shortening” effect caused by the mirror purge flows. The wall loss for HONO was estimated to be 2.0?% via a HONO standard generator. Measurement precisions (2 σ ) for HONO and NOsub2/sub are about 180 and 340?ppt in 30?s, respectively. A field inter-comparison was carried out at a rural suburban site in Wangdu, Hebei Province, China. The concentrations of HONO and NOsub2/sub measured by IBBCEAS were compared with a long optical path absorption photometer (LOPAP) and a NOsubx/sub analyzer (Thermo Fisher Electron Model 42i), and the results showed very good agreement, with correlation coefficients ( Rsup2/sup ) of HONO and NOsub2/sub being ～0.89 and ～0.95 , respectively; in addition, vehicle deployments were also tested to enable mobile measurements of HONO and NOsub2/sub , demonstrating the promising potential of using IBBCEAS for in situ, sensitive, accurate and fast simultaneous measurements of HONO and NOsub2/sub in the future.