Spatial and temporal variability of urban fluxes of methane, carbon monoxide and carbon dioxide above London, UK

We report on more than 3 years of measurements of fluxes of methane (CH4), carbon monoxide (CO) and carbon dioxide (CO2) taken by eddy-covariance in central London, UK. Mean annual emissions of CO2 in the period 2012–2014 (39.1 ± 2.4 ktons km−2 yr−1) and CO (89 ± 16 tons km−2 yr−1 ) were consistent (within 1 and 5% respectively) with values from the London Atmospheric Emissions Inventory, but measured CH4 emissions (72 ± 3 tons km−2 yr−1) were over two-fold larger than the inventory value. Seasonal variability was large for CO with a winter to summer reduction of 69 %, and monthly fluxes were strongly anti-correlated with mean air temperature. The winter increment in CO emissions was attributed mainly to vehicle cold starts and reduced fuel combustion efficiency. CO2 fluxes were 33 % higher in winter than in summer and anti-correlated with mean air temperature, albeit to a lesser extent than for CO. This was attributed to an increased demand for natural gas for heating during the winter. CH4 fluxes exhibited moderate seasonality (21 % larger in winter), and a spatially variable linear anti-correlation with air temperature. Differences in resident population within the flux footprint explained up to 90 % of the spatial variability of the annual CO2 fluxes and up to 99 % for CH4. Furthermore, we suggest that biogenic sources of CH4, such as wastewater, which is unaccounted for by the atmospheric emissions inventories, make a substantial contribution to the overall bud- get and that commuting dynamics in and out of central business districts could explain some of the spatial and temporal variability of CO2 and CH4 emissions. To our knowledge,this study is unique given the length of the data sets presented, especially for CO and CH4 fluxes. This study offers an independent assessment of “bottom-up” emissions inventories and demonstrates that the urban sources of CO and CO2 are well characterized in London. This is however not the case for CH4 emissions which are heavily underestimated by the inventory approach. Our results and others point to opportunities in the UK and abroad to identify and quantify the “missing” sources of urban methane, revise the methodologies of the emission inventories and devise emission reduction strategies for this potent greenhouse gas

Inter-annual trends of ultrafine particles in urban Europe

Ultrafine particles (UFP, those with diameters ≤ 100 nm), have been reported to potentially penetrate deeply into the respiratory system, translocate through the alveoli, and affect various organs, potentially correlating with increased mortality. The aim of this study is to assess long-term trends (5–11 years) in mostly urban UFP concentrations based on measurements of particle number size distributions (PNSD). Additionally, concentrations of other pollutants and meteorological variables were evaluated to support the interpretations. PNSD datasets from 12 urban background (UB), 5 traffic (TR), 3 suburban background (SUB) and 1 regional background (RB) sites in 15 European cities and 1 in the USA were evaluated. The non-parametric Theil-Sen's method was used to detect monotonic trends. Meta-analyses were carried out to assess the overall trends and those for different environments. The results showed significant decreases in NO, NO2, BC, CO, and particle concentrations in the Aitken (25–100 nm) and the Accumulation (100–800 nm) modes, suggesting a positive impact of the implementation of EURO 5/V and 6/VI vehicle standards on European air quality. The growing use of Diesel Particle Filters (DPFs) might also have clearly reduced exhaust emissions of BC, PM, and the Aitken and Accumulation mode particles. However, as reported by prior studies, there remains an issue of poor control of Nucleation mode particles (smaller than 25 nm), which are not fully reduced with current DPFs, without emission controls for semi-volatile organic compounds, and might have different origins than road traffic. Thus, contrasting trends for Nucleation mode particles were obtained across the cities studied. This mode also affected the UFP and total PNC trends because of the high proportion of Nucleation mode particles in both concentration ranges. It was also found that the urban temperature increasing trends might have also influenced those of PNC, Nucleation and Aitken modes.</p

Recommendations for reporting equivalent black carbon (eBC) mass concentrations based on long-term pan-European in-situ observations

A reliable determination of equivalent black carbon (eBC) mass concentrations derived from filter absorption photometers (FAPs) measurements depends on the appropriate quantification of the mass absorption cross-section (MAC) for converting the absorption coefficient (babs) to eBC. This study investigates the spatial–temporal variability of the MAC obtained from simultaneous elemental carbon (EC) and babs measurements performed at 22 sites. We compared different methodologies for retrieving eBC integrating different options for calculating MAC including: locally derived, median value calculated from 22 sites, and site-specific rolling MAC. The eBC concentrations that underwent correction using these methods were identified as LeBC (local MAC), MeBC (median MAC), and ReBC (Rolling MAC) respectively. Pronounced differences (up to more than 50 %) were observed between eBC as directly provided by FAPs (NeBC; Nominal instrumental MAC) and ReBC due to the differences observed between the experimental and nominal MAC values. The median MAC was 7.8 ± 3.4 m2 g-1 from 12 aethalometers at 880 nm, and 10.6 ± 4.7 m2 g-1 from 10 MAAPs at 637 nm. The experimental MAC showed significant site and seasonal dependencies, with heterogeneous patterns between summer and winter in different regions. In addition, long-term trend analysis revealed statistically significant (s.s.) decreasing trends in EC. Interestingly, we showed that the corresponding corrected eBC trends are not independent of the way eBC is calculated due to the variability of MAC. NeBC and EC decreasing trends were consistent at sites with no significant trend in experimental MAC. Conversely, where MAC showed s.s. trend, the NeBC and EC trends were not consistent while ReBC concentration followed the same pattern as EC. These results underscore the importance of accounting for MAC variations when deriving eBC measurements from FAPs and emphasize the necessity of incorporating EC observations to constrain the uncertainty associated with eBC.</p

European aerosol phenomenology - 8 : Harmonised source apportionment of organic aerosol using 22 Year-long ACSM/AMS datasets

Organic aerosol (OA) is a key component of total submicron particulate matter (PM1), and comprehensive knowledge of OA sources across Europe is crucial to mitigate PM1 levels. Europe has a well-established air quality research infrastructure from which yearlong datasets using 21 aerosol chemical speciation monitors (ACSMs) and 1 aerosol mass spectrometer (AMS) were gathered during 2013-2019. It includes 9 non-urban and 13 urban sites. This study developed a state-of-the-art source apportionment protocol to analyse long-term OA mass spectrum data by applying the most advanced source apportionment strategies (i.e., rolling PMF, ME-2, and bootstrap). This harmonised protocol was followed strictly for all 22 datasets, making the source apportionment results more comparable. In addition, it enables quantification of the most common OA components such as hydrocarbon-like OA (HOA), biomass burning OA (BBOA), cooking-like OA (COA), more oxidised-oxygenated OA (MO-OOA), and less oxidised-oxygenated OA (LO-OOA). Other components such as coal combustion OA (CCOA), solid fuel OA (SFOA: mainly mixture of coal and peat combustion), cigarette smoke OA (CSOA), sea salt (mostly inorganic but part of the OA mass spectrum), coffee OA, and ship industry OA could also be separated at a few specific sites. Oxygenated OA (OOA) components make up most of the submicron OA mass (average = 71.1%, range from 43.7 to 100%). Solid fuel combustion-related OA components (i.e., BBOA, CCOA, and SFOA) are still considerable with in total 16.0% yearly contribution to the OA, yet mainly during winter months (21.4%). Overall, this comprehensive protocol works effectively across all sites governed by different sources and generates robust and consistent source apportionment results. Our work presents a comprehensive overview of OA sources in Europe with a unique combination of high time resolution (30-240 min) and long-term data coverage (9-36 months), providing essential information to improve/validate air quality, health impact, and climate models.Peer reviewe

Measurement of NOx fluxes from a tall tower in central London, UK and comparison with emissions inventories

Direct measurements of NOx concentration and flux were made from a tall tower in central London, UK as part of the Clean Air for London (ClearfLo) project. Fast time resolution (10 Hz) NO and NO2 concentrations were measured and combined with fast vertical wind measurements to provide top-down flux estimates using the eddy covariance technique. Measured NOx fluxes were usually positive and ranged from close to zero at night to 2000–8000 ng m–2 s–1 during the day. Peak fluxes were usually observed in the morning, coincident with the maximum traffic flow. Measurements of the NOx flux have been scaled and compared to the UK National Atmospheric Emissions Inventory (NAEI) estimate of NOx emission for the measurement footprint. The measurements are on average 80% higher than the NAEI emission inventory for all of London. Observations made in westerly airflow (from parts of London where traffic is a smaller fraction of the NOx source) showed a better agreement on average with the inventory. The observations suggest that the emissions inventory is poorest at estimating NOx when traffic is the dominant source, in this case from an easterly direction from the BT Tower. Agreement between the measurements and the London Atmospheric Emissions Inventory (LAEI) are better, due to the more explicit treatment of traffic flow by this more detailed inventory. The flux observations support previous tailpipe observations of higher NOx emitted from the London vehicle diesel fleet than is represented in the NAEI or predicted for several EURO emission control technologies. Higher-than-anticipated vehicle NOx is likely responsible for the significant discrepancies that exist in London between observed NOx and long-term NOx projections

Field and laboratory evaluation of a high time resolution x-ray fluorescence instrument for determining the elemental composition of ambient aerosols

Measuring the chemical composition of airborne particulate matter (PM) can provide valuable information on the concentration of regulated toxic metals, support modelling approaches for source detection and assist in the identification and validation of abatement techniques. Undertaking these at a high time resolution (1 h or less) enables receptor modelling techniques to be more robustly linked to emission processes. This study describes a comprehensive laboratory and field evaluation of a high time resolution x-ray fluorescence (XRF) instrument (CES XACT 625) for a range of elements (As, Ba, Ca, Cd, Ce, Cl, Cr, Cu, Fe, K, Mn, Mo, Ni, Pb, Pt, S, Sb, Se, Si, Sr, Ti, V and Zn) against alternative techniques: high time resolution mass measurements, high time resolution ion chromatography, aerosol mass spectrometry, and established filter-based, laboratory analysis using inductively coupled plasma mass spectrometry (ICP-MS). Laboratory evaluation was carried out using a novel mass-based calibration technique to independently assess the accuracy of the XRF against laboratory generated aerosols, which resulted in slopes that were not significantly different from unity. This demonstrated that generated particles can serve as an alternative calibration method for this instrument.The XACT was evaluated in three contrasting field deployments; a heavily trafficked roadside site (PM10 and PM2.5), an industrial location downwind of a nickel refinery (PM10) and an urban background location influenced by nearby industries and motorways (PM10). The XRF technique agreed well with the ICP-MS measurements of daily filter samples in all cases with a median R2 of 0.93 and a median slope of 1.07 for the elements As, Ba, Ca, Cr, Cu, Fe, K, Mn, Ni, Pb, Se, Sr, Ti, V and Zn. Differences in the results were attributed to a combination of inlet location and sampling temperature, variable blank levels in filter paper and recovery rates from acid digestion. The XRF technique also agreed well with the other high time resolution measurements but showed a clear positive difference (slopes between 1.41 and 4.6), probably due to differences in the size selection methodology, volatility and water solubility of the PM in aerosol mass spectrometry (SO4) and ion chromatography (Ca, Cl, K and SO4), respectively.A novel filter analysis technique using the XACT showed promising initial results: filters analysed off-line with the XACT compared well to in situ XACT measurements with a median R2 of 0.96 and median slope of 1.07. The resulting range of slopes was comparable to slopes produced in the ICP-MS comparison. This technique provides an opportunity to use the XACT when it is not deployed in the field; thus expanding the potential use of this instrument in future studies.</ol

Source identification of the elemental fraction of particulate matter using size segregated, highly time-resolved data and an optimized source apportionment approach

Source emissions with high covariance degrade the performance of multivariate models, and often highly-time resolved data is needed to accurately extract the contribution of different emissions. Here, we use highly time-resolved size segregated elemental composition data to apportion the sources of the elemental fraction of PM in Zürich (May 2019–May 2020). For data collection, we have used an ambient metals monitor, Xact 625i, equipped with a sampling inlet alternating between PM2.5 and PM10. By implementing interpolation and a newly proposed uncertainty estimation methodology, it was possible to obtain and use in PMF a combined dataset of PM2.5 and PMcoarse (PM10-2.5) having data from only one instrument. The combination of the inlet switching system, the instrument's high time resolution, and the use of advanced source apportionment approaches yielded improved source apportionment results in terms of the number of identified sources, as the model, additionally to the diurnal and seasonal variation of the dataset, also utilizes the variation from the size segregated data. Thirteen sources of elements were identified, i.e., sea salt (5.4%), biomass burning (7.2%), construction (4.3%), industrial (3.3%), light-duty vehicles (5.4%), Pb (0.7%), Zn (0.7%), dust (22.1%), transported dust (9.5%), sulfates (15.4%), heavy-duty vehicles (17%), railway (6.6%) and fireworks (2.4%). The Covid-19 lockdown effect in PM sources in the area was also quantified. High-intensity events disproportionally affect the PMF solution, and in many cases, they are getting discarded before analysis, removing thus valuable information from the dataset. In this study, a three-step source apportionment approach was used to get a well-resolved unmixed solution when firework data points were included in the analysis. This approach can also be used for other sources and/or events with very high contributions that distort source apportionment analysis. Optimized source apportionment techniques are necessary for effective air pollution monitoring