Abstract. We report on the development of a cavityenhanced aerosol single-scattering albedometer based on incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) combined with an integrating sphere (IS) for simultaneous in situ measurements of aerosol scattering and extinction coefficients in an exact same sample volume. The cavity-enhanced albedometer employed a blue light-emitting-diode (LED)-based IBBCEAS approach for the measurement of wavelength-resolved aerosol optical extinction over the spectral range of 445-480 nm and an integrating sphere nephelometer coupled to the IBBCEAS setup for the measurement of aerosol scattering. The scattering signal was measured with a single-channel photomultiplier tube (PMT), providing an averaged value over a narrow bandwidth (full-width at half-maximum, FWHM, ∼ 9 nm) in the spectral region of 465-474 nm. A scattering coefficient at a wavelength of 470 nm was deduced as an averaged scattering value over the spectral region of 465-474 nm and used for data analysis and instrumental performance comparison. Performance evaluation of the albedometer was carried out using laboratory-generated particles and ambient aerosol. The scattering and extinction measurements of monodisperse polystyrene latex (PSL) spheres generated in the laboratory proved excellent correlation between two channels of the albedometer. The retrieved refractive index (RI) of the PSL particles from the measured scattering and extinction efficiencies agreed well with the values reported in previously published papers. Aerosol light scattering and extinction coefficients, single-scattering albedo (SSA) and NO 2 concentrations in an ambient sample were directly and simultaneously measured using the albedometer developed. The instrument developed was validated via an intercomparison of the measured aerosol scattering coefficients and NO 2 trace gas concentrations to a TSI 3563 integrating nephelometer and a chemiluminescence detector, respectively.

Abstract. Particulate matter (PM) pollution in China is an emerging environmental issue which policy makers and the public have increasingly paid attention to. In order to investigate the characteristics, sources, and chemical processes of PM pollution in Guangzhou, field measurements were conducted from 20 November 2017 to 5 January 2018, with a time-of-flight aerosol chemical speciation monitor (ToF-ACSM) and other collocated instruments. Mass concentrations of non-refractory submicron particulate matter (NR-PM1) measured by the ToF-ACSM correlated well with those of PM2.5 or PM1.1 measured by filter-based methods. The organic mass fraction increased from 45 % to 53 % when the air switched from non-pollution periods to pollution episodes (EPs), indicating significant roles of organic aerosols (OAs) during the whole study. Based on the mass spectra measured by the ToF-ACSM, positive matrix factorization (PMF) with the multilinear engine (ME-2) algorithm was performed to deconvolve OA into four factors, including hydrocarbon-like OA (HOA, 12 %), cooking OA (COA, 18 %), semi-volatile oxygenated OA (SVOOA, 30 %), and low-volatility oxygenated OA (LVOOA, 40 %). Furthermore, we found that SVOOA and nitrate were significantly contributed from local traffic emissions while sulfate and LVOOA were mostly attributed to regional pollutants. Comparisons between this work and other previous studies in China show that secondary organic aerosol (SOA) fraction in total OA increases spatially across China from the north to the south. Two distinctly opposite trends for NR-PM1 formation were observed during non-pollution periods and pollution EPs. The ratio of secondary PM (SPM = SVOOA + LVOOA + sulfate + nitrate + ammonium) to primary PM (PPM = HOA + COA + chloride), together with peroxy radicals RO2∗ and ozone, increased with increasing NR-PM1 concentration during non-pollution periods, while an opposite trend of these three quantities was observed during pollution EPs. Furthermore, oxidation degrees of both OA and SOA were investigated using the f44∕f43 space and the results show that at least two OOA factors are needed to cover a large range of f44 and f43 in Guangzhou. Comparisons between our results and other laboratory studies imply that volatile organic compounds (VOCs) from traffic emissions, in particular from diesel combustion and aromatic compounds, are the most likely SOA precursors in Guangzhou. Peroxy radical RO2∗ was used as a tracer for SOA formed through gas-phase oxidation. For non-pollution periods, SOA concentration was reasonably correlated with RO2∗ concentration during both daytime and nighttime, suggesting that gas-phase oxidation was primarily responsible for SOA formation. However, there was no correlation between SOA and RO2∗ in pollution EPs, suggesting a dramatically changed mechanism for SOA formation. This conclusion can also be supported by different features of SOA in a van Krevelen diagram between non-pollution periods and pollution EPs. Furthermore, for pollution EPs, when NR-PM1 mass concentration was divided into six segments, in each segment except for the lowest one SOA concentration was correlated moderately with RO2∗ concentration, suggesting that gas-phase oxidation still plays important roles in SOA formation. The intercepts of the above linear regressions, which likely correspond to the extent of other mechanisms (i.e., heterogeneous and multiphase reactions), increase with increasing NR-PM1 mass concentration. Our results suggest that while gas-phase oxidation contributes predominantly to SOA formation during non-pollution periods, other mechanisms such as heterogeneous and multiphase reactions play more important roles in SOA formation during pollution EPs than gas-phase oxidation.

This article describes the development and field application of a portable broadband cavity enhanced spectrometer (BBCES) operating in the spectral range of 440-480 nm for sensitive, real-time, in situ measurement of ambient glyoxal (CHOCHO) and nitrogen dioxide (NO). The instrument utilized a custom cage system in which the same SMA collimators were used in the transmitter and receiver units for coupling the LED light into the cavity and collecting the light transmitted through the cavity. This configuration realised a compact and stable optical system that could be easily aligned. The dimensions and mass of the optical layer were 676 × 74 × 86 mm and 4.5 kg, respectively. The cavity base length was about 42 cm. The mirror reflectivity at λ = 460 nm was determined to be 0.9998, giving an effective absorption pathlength of 2.26 km. The demonstrated measurement precisions (1σ) over 60 s were 28 and 50 pptv for CHOCHO and NO and the respective accuracies were 5% and 4%. By applying a Kalman adaptive filter to the retrieved concentrations, the measurement precisions of CHOCHO and NO were improved to 8 pptv and 40 pptv in 21 s.