Chemical composition of outdoor airborne particles at urban schools and possible implications for the air quality in classrooms

Vehicle emissions are a significant source of fine particles (Dp < 2.5 µm) in an urban environment. These fine particles have been shown to have detrimental health effects, with children thought to be more susceptible. Vehicle emissions are mainly carbonaceous in nature, and carbonaceous aerosols can be defined as either elemental carbon (EC) or organic carbon (OC). EC is a soot-like material emitted from primary sources while OC fraction is a complex mixture of hundreds of organic compounds from either primary or secondary sources (Cao et al., 2006). Therefore the ratio of OC/EC can aid in the identification of source. The purpose of this paper is to use the concentration of OC and EC in fine particles to determine the levels of vehicle emissions in schools. It is expected that this will improve the understanding of the potential exposure of children in a school environment to vehicle emissions

Evaluation of a low-cost optical particle counter (Alphasense OPC-N2) for ambient air monitoring

A fast growing area of research is the development of low-cost sensors for measuring air pollutants. The affordability and size of low-cost particle sensors makes them an attractive option for use in experiments requiring a number of instruments such as high density spatial mapping. However, for these low-cost sensors to be useful for these types of studies their accuracy and precision needs to be quantified. We evaluated the Alphasense OPC-N2, a promising low-cost miniature optical particle counter, for monitoring ambient airborne particles at typical urban background sites in the UK. The precision of the OPC-N2 was assessed by co-locating 14 instruments at a site to investigate the variation in measured concentrations. Comparison to two different reference optical particle counters as well as a TEOM-FDMS enabled the accuracy of the OPC-N2 to be evaluated. Comparison of the OPC-N2 to the reference optical instruments demonstrated reasonable agreement for the measured mass concentrations of PM1, PM2.5 and PM10. However, the OPC-N2 demonstrated a significant positive artefact in measured particle mass during times of high ambient RH (> 85 %) and a calibration factor was developed based upon κ-Kohler theory, using average bulk particle aerosol hygroscopicity. Application of this RH correction factor resulted in the OPC-N2 measurements being within 33 % of the TEOM-FDMS, comparable to the agreement between a reference optical particle counter and the TEOM-FDMS (20 %). Reasonable inter-unit precision for the 14 OPC-N2 sensors was observed. Overall, the OPC-N2 was found to accurately measure ambient airborne particle mass concentration provided they are i) correctly calibrated and ii) corrected for ambient RH. The reasonable level of precision demonstrated between multiple OPC-N2 suggests that they would be suitable device for applications where the spatial variability in particle concentration was to be determined

Evaluation of a low-cost optical particle counter (Alphasense OPC-N2) for ambient air monitoring

A fast-growing area of research is the development of low-cost sensors for measuring air pollutants. The affordability and size of low-cost particle sensors makes them an attractive option for use in experiments requiring a number of instruments such as high-density spatial mapping. However, for these low-cost sensors to be useful for these types of studies their accuracy and precision need to be quantified. We evaluated the Alphasense OPC-N2, a promising low-cost miniature optical particle counter, for monitoring ambient airborne particles at typical urban background sites in the UK. The precision of the OPC-N2 was assessed by co-locating 14 instruments at a site to investigate the variation in measured concentrations. Comparison to two different reference optical particle counters as well as a TEOM-FDMS enabled the accuracy of the OPC-N2 to be evaluated. Comparison of the OPC-N2 to the reference optical instruments shows some limitations for measuring mass concentrations of PM1, PM2.5 and PM10. The OPC-N2 demonstrated a significant positive artefact in measured particle mass during times of high ambient RH (>85%) and a calibration factor was developed based upon °-Köhler theory, using average bulk particle aerosol hygroscopicity. Application of this RH correction factor resulted in the OPC-N2 measurements being within 33% of the TEOM-FDMS, comparable to the agreement between a reference optical particle counter and the TEOM-FDMS (20%). Inter-unit precision for the 14 OPC-N2 sensors of 22±13% for PM10 mass concentrations was observed. Overall, the OPC-N2 was found to accurately measure ambient airborne particle mass concentration provided they are (i) correctly calibrated and (ii) corrected for ambient RH. The level of precision demonstrated between multiple OPC-N2s suggests that they would be suitable devices for applications where the spatial variability in particle concentration was to be determined

Evidence for renoxification in the tropical marine boundary layer

We present 2 years of NOx observations from the Cape Verde Atmospheric Observatory located in the tropical Atlantic boundary layer. We find that NOx mixing ratios peak around solar noon (at 20-30pptV depending on season), which is counter to box model simulations that show a midday minimum due to OH conversion of NO2 to HNO3. Production of NOx via decomposition of organic nitrogen species and the photolysis of HNO3 appear insufficient to provide the observed noontime maximum. A rapid photolysis of nitrate aerosol to produce HONO and NO2, however, is able to simulate the observed diurnal cycle. This would make it the dominant source of NOx at this remote marine boundary layer site, overturning the previous paradigm according to which the transport of organic nitrogen species, such as PAN, is the dominant source. We show that observed mixing ratios (November-December 2015) of HONO at Cape Verde (∼ 3.5pptV peak at solar noon) are consistent with this route for NOx production. Reactions between the nitrate radical and halogen hydroxides which have been postulated in the literature appear to improve the box model simulation of NOx. This rapid conversion of aerosol phase nitrate to NOx changes our perspective of the NOx cycling chemistry in the tropical marine boundary layer, suggesting a more chemically complex environment than previously thought

HONO Measurement by Differential Photolysis

Nitrous acid (HONO) has been quantitatively measured in situ by differential photolysis at 385 and 395 nm, and subsequent detection as nitric oxide (NO) by the chemiluminescence reaction with ozone (O3). The technique has been evaluated by Fourier transform infrared (FT-IR) spectroscopy to provide a direct HONO measurement in a simulation chamber and compared side by side with a long absorption path optical photometer (LOPAP) in the field. The NO-O3 chemiluminescence technique is robust, well characterized, and capable of sampling at low pressure, whilst solid-state converter technology allows for unattended in situ HONO measurements in combination with fast time resolution and response

Interference from alkenes in chemiluminescent NOx measurements

Nitrogen oxides (NOx=NO + NO2) are critical intermediates in atmospheric chemistry and air pollution. NOx levels control the cycling and hence abundance of the primary atmospheric oxidants OH and NO3 and regulate the ozone production which results from the degradation of volatile organic compounds (VOCs) in the presence of sunlight. They are also atmospheric pollutants, and NO2 is commonly included in air quality objectives and regulations. NOx levels also affect the production of the nitrate component of secondary aerosol particles and other pollutants, such as the lachrymator peroxyacetyl nitrate (PAN). The accurate measurement of NO and NO2 is therefore crucial for air quality monitoring and understanding atmospheric composition. The most commonly used approach for the measurement of NO is the chemiluminescent detection of electronically excited NO2 (NO∗2) formed from the NO + O3 reaction within the NOx analyser. Alkenes, ubiquitous in the atmosphere from biogenic and anthropogenic sources, also react with ozone to produce chemiluminescence and thus may contribute to the measured NOx signal. Their ozonolysis reaction may also be sufficiently rapid that their abundance in conventional instrument background cycles, which also utilises the reaction with ozone, differs from that in the measurement cycle such that the background subtraction is incomplete, and an interference effect results. This interference has been noted previously, and indeed, the effect has been used to measure both alkenes and ozone in the atmosphere. Here we report the results of a systematic investigation of the response of a selection of commercial NOx monitors to a series of alkenes. These NOx monitors range from systems used for routine air quality monitoring to atmospheric research instrumentation. The species-investigated range was from short-chain alkenes, such as ethene, to the biogenic monoterpenes. Experiments were performed in the European PHOtoREactor (EUPHORE) to ensure common calibration and samples for the monitors and to unequivocally confirm the alkene levels present (via Fourier transform infrared spectroscopy - FTIR). The instrument interference responses ranged from negligible levels up to 11 %, depending upon the alkene present and conditions used (e.g. the presence of co-reactants and differing humidity). Such interferences may be of substantial importance for the interpretation of ambient NOx data, particularly for high VOC, low NOx environments such as forests or indoor environments where alkene abundance from personal care and cleaning products may be significant

Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer

Recent field studies have suggested that sea-salt particulate nitrate (NITs) photolysis may act as a significant local source of nitrogen oxides (NOx) over oceans. We present a study of the global impact of this process on oxidant concentrations in the marine boundary layer (MBL) using the GEOS-Chem model, after first updating the model to better simulate observed gas-particle phase partitioning of nitrate in the marine boundary layer. Model comparisons with long-term measurements of NOx from the Cape Verde Atmospheric Observatory (CVAO) in the eastern tropical North Atlantic provide support for an in situ source of NOx from NITs photolysis, with NITs photolysis coefficients about 25-50 times larger than corresponding HNO3 photolysis coefficients. Short-term measurements of nitrous acid (HONO) at this location show a clear daytime peak, with average peak mixing ratios ranging from 3 to 6 pptv. The model reproduces the general shape of the diurnal HONO profile only when NITs photolysis is included, but the magnitude of the daytime peak mixing ratio is under-predicted. This under-prediction is somewhat reduced if HONO yields from NITs photolysis are assumed to be close to unity. The combined NOx and HONO analysis suggests that the upper limit of the ratio of NITs : HNO3 photolysis coefficients is about 100. The largest simulated relative impact of NITs photolysis is in the tropical and subtropical marine boundary layer, with peak local enhancements ranging from factors of 5 to 20 for NOx, 1.2 to 1.6 for OH, and 1.1 to 1.3 for ozone. Since the spatial extent of the sea-salt aerosol (SSA) impact is limited, global impacts on NOx, ozone, and OH mass burdens are small ( ∼ 1-3 %). We also present preliminary analysis showing that particulate nitrate photolysis in accumulation-mode aerosols (predominantly over continental regions) could lead to ppbv-level increases in ozone in the continental boundary layer. Our results highlight the need for more comprehensive long-term measurements of NOx, and related species like HONO and sea-salt particulate nitrate, to better constrain the impact of particulate nitrate photolysis on marine boundary layer oxidant chemistry. Further field and laboratory studies on particulate nitrate photolysis in other aerosol types are also needed to better understand the impact of this process on continental boundary layer oxidant chemistry

Source apportionment of fine and coarse particles at a roadside and urban background site in London during the 2012 summer ClearfLo campaign

AbstractLondon, like many major cities, has a noted air pollution problem, and a better understanding of the sources of airborne particles in the different size fractions will facilitate the implementation and effectiveness of control strategies to reduce air pollution. Thus, the trace elemental composition of the fine and coarse fraction were analysed at hourly time resolution at urban background (North Kensington, NK) and roadside (Marylebone Road, MR) sites within central London. Unlike previous work, the current study focuses on measurements during the summer providing a snapshot of contributing sources, utilising the high time resolution to improve source identification. Roadside enrichment was observed for a large number of elements associated with traffic emissions (Al, S, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Rb and Zr), while those elements that are typically from more regional sources (e.g. Na, Cl, S and K) were not found to have an appreciable increment. Positive Matrix Factorization (PMF) was applied for the source apportionment of the particle mass at both sites with similar sources being identified, including sea salt, airborne soil, traffic emissions, secondary inorganic aerosols and a Zn-Pb source. In the fine fraction, traffic emissions was the largest contributing source at MR (31.9%), whereas it was incorporated within an “urban background” source at NK, which had contributions from wood smoke, vehicle emissions and secondary particles. Regional sources were the major contributors to the coarse fraction at both sites. Secondary inorganic aerosols (which contained influences from shipping emissions and coal combustion) source factors accounted for around 33% of the PM10 at NK and were found to have the highest contributions from regional sources, including from the European mainland. Exhaust and non-exhaust sources both contribute appreciably to PM10 levels at the MR site, highlighting the continuing importance of vehicle-related air pollutants at roadside

Is the ocean surface a source of nitrous acid (HONO) in the marine boundary layer?

Nitrous acid, HONO, is a key net photolytic precursor to OH radicals in the atmospheric boundary layer. As OH is the dominant atmospheric oxidant, driving the removal of many primary pollutants and the formation of secondary species, a quantitative understanding of HONO sources is important to predict atmospheric oxidising capacity. While a number of HONO formation mechanisms have been identified, recent work has ascribed significant importance to the dark, ocean-surface-mediated conversion of NO2 to HONO in the coastal marine boundary layer. In order to evaluate the role of this mechanism, here we analyse measurements of HONO and related species obtained at two contrasting coastal locations - Cabo Verde (Atlantic Ocean, denoted Cape Verde herein), representative of the clean remote tropical marine boundary layer, and Weybourne (UK), representative of semi-polluted northern European coastal waters. As expected, higher average concentrations of HONO (70ppt) were observed in marine air for the more anthropogenically influenced Weybourne location compared to Cape Verde (HONO <5ppt). At both sites, the approximately constant HONO/NO2 ratio at night pointed to a low importance for the dark, ocean-surface-mediated conversion of NO2 into HONO, whereas the midday maximum in the HONO/NO2 ratios indicated significant contributions from photo-enhanced HONO formation mechanisms (or other sources). We obtained an upper limit to the rate coefficient of dark, ocean-surface HONO-to-NO2 conversion of CHONOCombining double low line0.0011ppbh-1 from the Cape Verde observations; this is a factor of 5 lower than the slowest rate reported previously. These results point to significant geographical variation in the predominant HONO formation mechanisms in marine environments and indicate that caution is required when extrapolating the importance of such mechanisms from individual study locations to assess regional and/or global impacts on oxidising capacity. As a significant fraction of atmospheric processing occurs in the marine boundary layer, particularly in the tropics, better constraint of the possible ocean surface source of HONO is important for a quantitative understanding of chemical processing of primary trace gases in the global atmospheric boundary layer and associated impacts upon air pollution and climate

Measurement report: Interpretation of wide-range particulate matter size distributions in Delhi

Delhi is one of the world's most polluted cities, with very high concentrations of airborne particulate matter. However, little is known about the factors controlling the characteristics of wide-range particle number size distributions. Here, new measurements are reported from three field campaigns conducted in winter and pre-monsoon and post-monsoon seasons at the Indian Institute of Technology campus in the south of the city. Particle number size distributions were measured simultaneously, using a scanning mobility particle sizer and a GRIMM optical particle monitor, covering 15 nm to >10 μm diameter. The merged, wide-range size distributions were categorized into the following five size ranges: nucleation (15-20 nm), Aitken (20-100 nm), accumulation (100 nm-1 μm), large fine (1-2.5 μm), and coarse (2.5-10 μm) particles. The ultrafine fraction (15-100 nm) accounts for about 52 % of all particles by number (PN10 is the total particle number from 15 nm to 10 μm) but just 1 % by PM10 volume (PV10 is the total particle volume from 15 nm to 10 μm). The measured size distributions are markedly coarser than most from other parts of the world but are consistent with earlier cascade impactor data from Delhi. Our results suggest substantial aerosol processing by coagulation, condensation, and water uptake in the heavily polluted atmosphere, which takes place mostly at nighttime and in the morning hours. Total number concentrations are highest in winter, but the mode of the distribution is largest in the post-monsoon (autumn) season. The accumulation mode particles dominate the particle volume in autumn and winter, while the coarse mode dominates in summer. Polar plots show a huge variation between both size fractions in the same season and between seasons for the same size fraction. The diurnal pattern of particle numbers is strongly reflective of a road traffic influence upon concentrations, especially in autumn and winter, although other sources, such as cooking and domestic heating, may influence the evening peak. There is a clear influence of diesel traffic at nighttime, when it is permitted to enter the city, and also indications in the size distribution data of a mode < 15 nm, which is probably attributable to CNG/LPG vehicles. New particle formation appears to be infrequent and is, in this dataset, limited to 1 d in the summer campaign. Our results reveal that the very high emissions of airborne particles in Delhi, particularly from traffic, determine the variation in particle number size distributions