ALBERT

Description: Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an intercomparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available a long-path absorption photometer (LOPAP) and a custom-built instrument) and two broadband cavity-enhanced absorption spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) and a selected ion flow tube mass spectrometer (SIFT-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends and variability in HONO (r2 〉 0.97), yet they displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher overall than the BBCEAS systems by between 12 % and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location and/or inlet position, but this observation may have been more associative than casual.

Description: Nitrous acid (HONO) is a key determinant of the daytime radical budget in the daytime boundary layer, with quantitative measurement required to understand OH radical abundance. Accurate and precise measurements of HONO are therefore needed; however HONO is a challenging compound to measure in the field, in particular in a chemically complex and highly polluted environment. Here we report an inter-comparison exercise between HONO measurements performed by two wet chemical techniques (the commercially available LOPAP and a custom-built instrument) and two Broadband Cavity Enhanced Absorption Spectrophotometer (BBCEAS) instruments at an urban location in Beijing. In addition, we report a comparison of HONO measurements performed by Time of Flight Chemical Ionization Mass Spectrometer (ToF-CIMS) and Syft Proton Transfer Reaction Mass Spectrometer (PTR-MS) to the more established techniques (wet chemical and BBCEAS). The key finding from the current work was that all instruments agree on the temporal trends/variability in HONO (r2 〉 0.97), yet displayed some divergence in absolute concentrations, with the wet chemical methods consistently higher than the BBCEAS systems by between 12 and 39 %. We found no evidence for any systematic bias in any of the instruments, with the exception of measurements near instrument detection limits. The causes of the divergence in absolute HONO concentrations were unclear, and may in part have been due to spatial variability, i.e. differences in instrument location/inlet position.

Description: There is considerable interest in using low-cost optical particle counters (OPCs) to supplement existing routine air quality networks that monitor particle mass concentrations. In order to do this, low-cost OPC data need to be comparable with particle mass reference instrumentation; however, there is currently no widely agreed upon methodology to accomplish this. Aerosol hygroscopicity is known to be a key parameter to consider when correcting particle mass concentrations derived from low-cost OPCs, particularly at high ambient relative humidity (RH). Correction factors have been developed that apply κ-Köhler theory to correct for the influence of water uptake by hygroscopic aerosols. We have used datasets of co-located reference particle measurements and low-cost OPC (OPC-N2, Alphasense) measurements, collected in four cities on three continents, to explore the performance of this correction factor. We provide evidence that the elevated particle mass concentrations, reported by the low-cost OPC relative to reference instrumentation, are due to bulk aerosol hygroscopicity under different RH conditions, which is determined by aerosol composition and, in particular, the levels of hygroscopic aerosols (sulfate and nitrate). We exploit measurements made in volcanic plumes in Nicaragua, which are predominantly composed of sulfate aerosol, as a natural experiment to demonstrate this behaviour in the ambient atmosphere; the observed humidogram from these measurements closely resembles the calculated pure sulfuric acid humidogram. The results indicate that the particle mass concentrations derived from low-cost OPCs during periods of high RH (〉60 %) need to be corrected for aerosol hygroscopic growth. We employed a correction factor based on κ-Köhler theory and observed that the corrected OPC-N2 PM2.5 mass concentrations were within 33 % of reference measurements at all sites. The results indicated that a κ value derived in situ (using suitable reference instrumentation) would lead to the most accurate correction relative to co-located reference instruments. Applying a κ values from the literature in the correction factor also resulted in improved OPC-N2 performance, with the measurements being within 50 % of the reference values. Therefore, for areas where suitable reference instrumentation for developing a local correction factor is lacking, using a literature κ value can result in a reasonable correction. For locations with low levels of hygroscopic aerosols and low RH values, a simple calibration against gravimetric measurements (using suitable reference instrumentation) would likely be sufficient. Whilst this study generated correction factors specific for the Alphasense OPC-N2 sensor, the calibration methodology developed is likely amenable to other low-cost PM sensors.