Urban Plume Research Articles

The regional impact of urban emissions on air quality in Europe: the role of the urban canopy effects

Abstract. Urban areas are hot spots of intense emissions, and they influence air quality not only locally but on a regional or even global scale. The impact of urban emissions over different scales depends on the dilution and chemical transformation of the urban plumes which are governed by the local- and regional-scale meteorological conditions. These are influenced by the presence of urbanized land surface via the so-called urban canopy meteorological forcing (UCMF). In this study, we investigate for selected central European cities (Berlin, Budapest, Munich, Prague, Vienna and Warsaw) how the urban emission impact (UEI) is modulated by the UCMF for present-day climate conditions (2015–2016) using two regional climate models, the regional climate models RegCM and Weather Research and Forecasting model coupled with Chemistry (WRF-Chem; its meteorological part), and two chemistry transport models, Comprehensive Air Quality Model with Extensions (CAMx) coupled to either RegCM and WRF and the “chemical” component of WRF-Chem. The UCMF was calculated by replacing the urbanized surface by a rural one, while the UEI was estimated by removing all anthropogenic emissions from the selected cities. We analyzed the urban-emission-induced changes in near-surface concentrations of NO2, O3 and PM2.5. We found increases in NO2 and PM2.5 concentrations over cities by 4–6 ppbv and 4–6 µg m−3, respectively, meaning that about 40 %–60 % and 20 %–40 % of urban concentrations of NO2 and PM2.5 are caused by local emissions, and the rest is the result of emissions from the surrounding rural areas. We showed that if UCMF is included, the UEI of these pollutants is about 40 %–60 % smaller, or in other words, the urban emission impact is overestimated if urban canopy effects are not taken into account. In case of ozone, models due to UEI usually predict decreases of around −2 to −4 ppbv (about 10 %–20 %), which is again smaller if UCMF is considered (by about 60 %). We further showed that the impact on extreme (95th percentile) air pollution is much stronger, and the modulation of UEI is also larger for such situations. Finally, we evaluated the contribution of the urbanization-induced modifications of vertical eddy diffusion to the modulation of UEI and found that it alone is able to explain the modeled decrease in the urban emission impact if the effects of UCMF are considered. In summary, our results showed that the meteorological changes resulting from urbanization have to be included in regional model studies if they intend to quantify the regional footprint of urban emissions. Ignoring these meteorological changes can lead to the strong overestimation of UEI.

A numerical study of the urban green roof and cool roof strategies’ effects on boundary layer meteorology and ozone air quality in a megacity

Green roof and cool roof are two popular strategies to mitigate urban heat island especially in the summer time. The meteorological effect (cooling on the near surface temperature) of the two mitigation strategies has been proved by lots of studies while the environmental effect (effect on urban air quality) is still largely unknown. In this paper the WRF-Chem model coupled with a single layer urban canopy model is used to simulate three heat wave and heavy ozone pollution episodes in Shanghai, China. Sensitivity experiments of green roof and cool roof are carried out and the results show that both green roof and cool roof can effectively mitigate urban heat island, and their cooling efficiencies are similar even their cooling mechanisms are different. All of them can reduce the lasting time and area of high temperature and extreme hot, but the ozone pollution may become more serious. According to the different ambient wind field and ozone distribution, these three ozone pollution episodes can be divided into two conditions: urban dome and urban plume. The decrease of urban surface temperature can inhibit the turbulent activities and reduce the height of the boundary layer; the concentration of ozone in urban Zone A (below 750 m height) increases, but decreases in urban Zone B (750 m-2km height) for urban dome. By calculating the ozone fluxes at different heights, we find that the urban heat island circulation can transport surface ozone into city, horizontally; while in Zone B, the horizontal divergence transport ozone out of the city, and green roof and cool roof can decrease the temperature difference between urban and suburban, which can inhibit this ozone transportation of urban heat island circulation.

Thermal modeling of a Swiss urban aquifer and implications for geothermal heat pump systems

The progressive electrification of the building conditioning sector in recent years has greatly contributed to reducing greenhouse gas emissions by using renewable energy sources, particularly shallow geothermal energy. This energy can be exploited through open and closed shallow geothermal systems (SGS), and their performances greatly depend on the ground/groundwater temperature, which can be affected by both natural and anthropogenic phenomena. The present study proposes an approach to characterize aquifers affected by high SGS exploitation (not simulated in this work). Characterization of the potential hydro/thermogeological natural state is necessary to understand the regional flow and heat transport, and to identify local thermal anomalies. Passive microseismic and groundwater monitoring were used to assess the shape and thermal status of the aquifer; numerical modeling in both steady-state and transient conditions allowed understanding of the flow and heat transport patterns. Two significant thermal anomalies were detected in a fluvio-glacial aquifer in southern Switzerland, one created by river water exfiltration and one of anthropogenic nature. A favorable time lag of 110 days between river and groundwater temperature and an urban hot plume produced by underground structures were observed. These thermal anomalies greatly affect the local thermal status of the aquifer and consequently the design and efficiency of current and future SGS. Results show that the correct characterization of the natural thermo-hydrogeological status of an aquifer is a fundamental basis for determining the impact of boundary conditions and to provide initial conditions required to perform reliable local thermal sustainability assessments, especially where high SGS exploitation occurs.

Characteristics and source apportionment of volatile organic compounds (VOCs) at a coastal site in Hong Kong

Volatile organic compounds (VOCs) that are emitted from biomass burning, vehicle exhaust, and industrial emissions play a vital role in the formation of ozone (O 3 ) and secondary organic aerosols (SOA). Since VOCs are the precursors of O 3 and aerosol pollution which have become the world's most emergent environmental problems, a field measurement study focused on VOCs was carried out from 27 August to 10 October 2018 in a rural coastal site in Hong Kong. During the campaign, 13 VOC species were detected continuously with proton-transfer-reaction quadrupole mass spectrometry, and their effects on photochemical air pollution were studied. Methanol was the most abundant species among the measured VOCs (average concentration, 3.73 ± 3.26 ppb), and higher concentrations of oxygenated VOCs were found than reported in previous studies of atmospheric chemistry in rural areas. Diurnal variations were observed in the concentrations of various VOC species, indicating that the VOC concentrations were influenced by photochemical reactions. The amount of O 3 formation was estimated based on the maximum incremental reactivity scale of the VOCs. The top five contributors to O 3 formation in Hong Kong (in order) were isoprene (13.46 μg/m 3 ), methyl ethyl ketone (12.74 μg/m 3 ), xylene (8.52 μg/m 3 ), acetaldehyde (8.22 μg/m 3 ), and acrolein (4.32 μg/m 3 ). Receptor model positive matrix factorization (PMF) was used to identify the dominant emission sources and evaluate their corresponding contributions to VOCs. Five major VOC sources were identified with the PMF method, including (1) industry and vehicle-related sources (8.1%), (2) biogenic emissions (5.5%), (3) biomass burning (63.7%), (4) secondary formation (9.2%), and (5) ship-related emissions (13.5%). The source apportionment results from PMF analysis show that the sampling site at the southeastern tip of Hong Kong was strongly influenced by urban plumes from the Guangdong–Hong Kong–Macao Greater Bay Area/Pearl River Delta region and by oceanic emissions. • VOCs concentrations were measured online by PTR-MS during autumn in Hong Kong. • OVOCs were the dominant species with potential for ozone formation. • The largest contributor to ambient VOCs was biomass burning during campaign. • The air pollution in Hong Kong was strongly influenced by urban plumes from GBA/PRD and by oceanic emissions.

Characterization of Aerosol Sources and Optical Properties in Siberia Using Airborne and Spaceborne Observations

Airborne backscatter lidar at 532 nm and in-situ measurements of black carbon (BC), carbon monoxide excess above background (ΔCO), and aerosol size distribution were carried out over Siberia in July 2013 and June 2017 in order to sample several kinds of aerosol sources. Aerosol types are derived using the Lagrangian FLEXible PARTicle dispersion model (FLEXPART) simulations and satellite observations. Six aerosol types could be identified in this work: (i) dusty aerosol mixture, (ii) Ob valley gas flaring emission, (iii) fresh forest fire, (iv) aged forest fire, (v) urban emissions over the Tomsk/Novosibirsk region (vi) long range transport of Northern China urban emission. The altitude range of aerosol layers is discussed for each aerosol type, showing transport above the boundary layer for long range transport of Northern China emissions or fresh forest fire. Comparisons of aerosol optical properties, BC and ΔCO are made between aged and fresh plumes for both the urban and forest fire emissions. An increase of aerosol optical depth at 532 nm (AOD532), aerosol particle size and ΔCO is found for aged forest fire plumes. Similar results are obtained when comparing the aged urban plume from Northern China with fresh urban emissions from Siberian cities. A flight above gas flaring emissions corresponds to the largest AOD532 and provides a possible range of 50–60 sr for the lidar ratio of these aerosol plumes often encountered in Siberia. Black carbon concentrations are relatively higher for the flaring plume (0.4–0.5 μμg.m−3) than for the urban plume (0.2 μμg.m−3). The largest BC concentrations are found for the fresh forest fire plume. The aerosol type identification and AOD532 provided by CALIOP Version 4.2 data products in air masses with similar origin generally agree with the results obtained from our detailed analysis of the aerosol plume origins.

Coupling an online ion conductivity measurement with the particle-into-liquid sampler: Evaluation and modeling using laboratory and field aerosol data.

A particle-into-liquid sampler (PILS) was coupled to a flow-through conductivity cell to provide a continuous, nondestructive, online measurement in support of offline ion chromatography analysis. The conductivity measurement provides a rapid assessment of the total ion concentration augmenting slower batch-sample data from offline analysis and is developed primarily to assist airborne measurements, where fast time-response is essential. A conductivity model was developed for measured ions and excellent closure was derived for laboratory-generated aerosols (97% conductivity explained, R2 > 0.99). The PILS-conductivity measurement was extensively tested throughout the NASA Cloud, Aerosol and Monsoon Processes: Philippines Experiment (CAMP2Ex) during nineteen research flights. A diverse range of ambient aerosol was sampled from biomass burning, fresh and aged urban pollution, and marine sources. Ambient aerosol did not exhibit the same degree of closure as the laboratory aerosol, with measured ions only accountable for 43% of the conductivity. The remaining fraction of the conductivity was examined in combination with ion charge balance and found to provide additional supporting information for diagnosing and modeling particle acidity. An urban plume case study was used to demonstrate the utility of the measurement for supplementing compositional data and augmenting the temporal capability of the PILS.

Statistical urban plume analysis using observations and air mass modelling at a rural station in the northern Spanish plateau

The influence of urban plumes on the final measurements recorded at rural stations is an issue which has rarely been touched upon in great detail. A better knowledge of local and regional sources of atmospheric CO2 and CH4 evolution over time and space provides policy-makers with the right awareness when acting to improve air quality. Assessing the links between air pollutant mixing ratios and wind direction data can help to identify possible sources. Using the Lagrangian METEX model, the current paper’s main motivation is to identify the impact of the Valladolid urban plume on the final CO2 and CH4 high-precision measurements recorded with a Picarro analyser at a rural station in the upper Spanish plateau (CIB station). The current paper is based on a statistical approach in which multiyear CO2 and CH4 observations are interpreted by means of different statistics and distribution functions. Higher values were detected for both CO2 and CH4 in southern sectors, showing the effect which the Valladolid plume has on final CO2 and CH4 measurements. In addition, six different distribution functions were applied to the dataset and provided satisfactory contrasts with experimental values obtained using Pearson correlation and r critical values. Results indicate that CO2 and CH4 data fitted the Gamma, the Gumbel, and the Lognormal distributions best.

Urban plume characteristics under various wind speed, heat flux, and stratification conditions

Abstract The adverse environmental impacts of the urban heat island (UHI) phenomenon have been known amid rapid urbanization in many parts of the world. UHI-induced circulation (UHIC) can affect pollutant dispersion and heat exchange. An UHIC can transform into an urban plume (or perturbed UHIC) in the presence of regional wind. To understand the urban plume characteristics, we apply the weather research and forecasting model to simulate UHIC in the presence of background wind. Particular attention is paid to settings with a buoyancy velocity ratio (R) of 2.0, the strong UHIC flow pattern is characterized by upstream back-currents and returned leeside inflows. For 0.5 3.0, and a transitional phase when R = 2.0–3.0. The stratification strength also influences the flow structures of urban plumes and pollutant dispersion. For example, stronger stratification with N = 0.014 s−1 prevents urban plumes from rising and contributes to the formation of returned leeside flow of urban plumes, resulting in a high tracer concentration over urban areas.

Exploration of oxidative chemistry and secondary organic aerosol formation in the Amazon during the wet season: explicit modeling of the Manaus urban plume with GECKO-A

Abstract. The GoAmazon 2014/5 field campaign took place in Manaus, Brazil, and allowed the investigation of the interaction between background-level biogenic air masses and anthropogenic plumes. We present in this work a box model built to simulate the impact of urban chemistry on biogenic secondary organic aerosol (SOA) formation and composition. An organic chemistry mechanism is generated with the Generator for Explicit Chemistry and Kinetics of Organics in the Atmosphere (GECKO-A) to simulate the explicit oxidation of biogenic and anthropogenic compounds. A parameterization is also included to account for the reactive uptake of isoprene oxidation products on aqueous particles. The biogenic emissions estimated from existing emission inventories had to be reduced to match measurements. The model is able to reproduce ozone and NOx for clean and polluted situations. The explicit model is able to reproduce background case SOA mass concentrations but does not capture the enhancement observed in the urban plume. The oxidation of biogenic compounds is the major contributor to SOA mass. A volatility basis set (VBS) parameterization applied to the same cases obtains better results than GECKO-A for predicting SOA mass in the box model. The explicit mechanism may be missing SOA-formation processes related to the oxidation of monoterpenes that could be implicitly accounted for in the VBS parameterization.

Estimation of NO<sub><i>x</i></sub> and SO<sub>2</sub> emissions from Sarnia, Ontario, using a mobile MAX-DOAS (Multi-AXis Differential Optical Absorption Spectroscopy) and a NO<sub><i>x</i></sub> analyzer

Abstract. Sarnia, Ontario, experiences pollutant emissions disproportionate to its relatively small size. The small size of the city limits traditional top-down emission estimate techniques (e.g., satellite) but a low-cost solution for emission monitoring is the mobile MAX-DOAS (Multi-AXis Differential Optical Absorption Spectroscopy). Measurements were made using this technique from 21 March 2017 to 23 March 2017 along various driving routes to retrieve vertical column densities (VCDs) of NO2 and SO2 and to estimate emissions of NOx and SO2 from the Sarnia region. A novel aspect of the current study was the installation of a NOx analyzer in the vehicle to allow real time measurement and characterization of near-surface NOx∕NO2 ratios across the urban plumes, allowing improved accuracy of NOx emission estimates. Confidence in the use of near-surface-measured NOx∕NO2 ratios for estimation of NOx emissions was increased by relatively well-mixed boundary layer conditions. These conditions were indicated by similar temporal trends in NO2 VCDs and mixing ratios when measurements were sufficiently distant from the sources. Leighton ratios within transported plumes indicated peroxy radicals were likely disturbing the NO–NO2–O3 photostationary state through VOC (volatile organic compound) oxidation. The average lower-limit emission estimate of NOx from Sarnia was 1.60±0.34 t h−1 using local 10 m elevation wind-speed measurements. Our estimates were larger than the downscaled annual 2017 NPRI-reported (National Pollution Release Inventory) industrial emissions of 0.9 t NOx h−1. Our lower-limit estimate of SO2 emissions from Sarnia was 1.81±0.83 t SO2 h−1, equal within uncertainty to the 2017 NPRI downscaled value of 1.85 t SO2 h−1. Satellite-derived NO2 VCDs over Sarnia from the ozone monitoring instrument (OMI) were lower than mobile MAX-DOAS VCDs, likely due to the large pixel size relative to the city's size. The results of this study support the utility of the mobile MAX-DOAS method for estimating NOx and SO2 emissions in relatively small, highly industrialized regions, especially when supplemented with mobile NOx measurements.

Sensitivity of Ozone Production to NOx and VOC Along the Lake Michigan Coastline

AbstractWe report on the sensitivity of enhanced ozone (O3) production, observed during lake breeze circulation along the coastline of Lake Michigan, to the concentrations of nitrogen oxides (NOx = NO + NO2) and volatile organic compounds (VOCs). We assess the sensitivity of O3 production to NOx and VOC on a high O3 day during the Lake Michigan Ozone Study 2017 using an observationally constrained chemical box model that implements the Master Chemical Mechanism (MCM v3.3.1) and recent emission inventories for NOx and VOCs. The Master Chemical Mechanism model is coupled to a backward air mass trajectory analysis from a ground supersite in Zion, IL, where an extensive series of measurements of O3 precursors and their oxidation products, including hydrogen peroxide (H2O2), nitric acid (HNO3), and particulate nitrates (NO3−) serve as model constraints. We evaluate the chemical evolution of the Chicago‐Gary urban plume as it advects over Lake Michigan and demonstrate how modeled indicators of VOC‐ versus NOx‐sensitive regimes can be constrained by measurements at the trajectory endpoint. Using the modeled ratio of the instantaneous H2O2 and HNO3 production rates (PH2O2/PHNO3), we suggest that O3 production over the urban source region is strongly VOC sensitive and progresses towards a more NOx‐sensitive regime as the plume advects north along the Lake Michigan coastline on this day. We also demonstrate that ground‐based measurements of the mean concentration ratio of H2O2 to HNO3 describe the sensitivity of O3 production to VOC and NOx as the integral of chemical production along the plume path.

Atmospheric Processing of Loess Particles in a Polluted Urban Area of Northwestern China

AbstractLoess is an important dust component of airborne particles in Northwestern China. Knowledge of the chemical composition, mixing state, and processing of loess particles in urban plumes is still limited. Urban loess particles were characterized using a single‐particle aerosol mass spectrometer. To understand sources and processing of loess particles, source samples from the road, urban background, soil, construction, and biomass burning ash were collected in the urban areas and characterized. Loess particles were determined as a kind of calcium‐silicate‐rich ones, which were internally mixed with calcium, silicates, potassium, elemental carbon, organics, ammonium, sulfate, and nitrate. Road and soil were major sources of loess particles. Among the aged loess particles, the average peak areas of taken‐up nitrate and sulfate were comparable to that of (Fe+Ca+Al). Diurnal uptake profiles of chloride, sulfate, oxalate, and nitrate on loess particles were analyzed. The nocturnal elevation of chloride occurred significantly due to the uptake of HCl (g). Nighttime nitrate formation occurred prevalently under high relative humidity conditions via the heterogeneous hydrolysis of N2O5. The nighttime enrichment of oxalate, which is a marker for aqueous‐formatted secondary organic aerosol, was also found. Besides the nighttime chemistry, the daytime photochemical activities were also a drive for the elevations of sulfate, nitrate, and ammonium. Conclusively, the processing of loess particles in polluted urban plumes significantly altered their chemical composition and mixing state.

Transport mechanism of urban plume dispersion

Winds (advection) and turbulence (diffusion) are the driving forces for urban plume dispersion whose partitioning is complicated by urban morphology and the conditions of atmospheric surface layer (ASL). Wind tunnel parametric tests are conducted to examine the plume behavior in the turbulent boundary layers (TBLs) over hypothetical buildings (roughness elements of ribs and bricks) with drag coefficient Cd (= 2uτ2/U∞2; where uτ and U∞ are, respectively, the friction velocity and the freestream velocity) varying from 4.7 × 10−3 to 10 × 10−3. Vehicular emission is modeled by atomizing water vapor via a ground-level line source in crossflows. The laboratory measurements show that the mean tracer concentrations ψ‾ exhibit the theoretical Gaussian form, supporting the classic plume dispersion framework. The horizontal advection tracer flux u‾ψ‾ dominates the transport processes compared with the vertical turbulent tracer flux w''ψ''‾. Increasing Cd leads to a decrease in u‾ψ‾ and an increase in w''ψ''‾ simultaneously, and vice versa. The changes in partitioning of transport processes in response to urban morphology imply that the conventional parameterization of dispersion coefficient σz (determined by atmospheric stability only) should be applied cautiously for urban setting. A new simple scheme of σz parameterization, which specifically accounts for the influence from urban roughness on the plume dispersion, is proposed.

Anthropogenic enhancements to production of highly oxygenated molecules from autoxidation

Atmospheric oxidation of natural and anthropogenic volatile organic compounds (VOCs) leads to secondary organic aerosol (SOA), which constitutes a major and often dominant component of atmospheric fine particulate matter (PM2.5). Recent work demonstrates that rapid autoxidation of organic peroxy radicals (RO2) formed during VOC oxidation results in highly oxygenated organic molecules (HOM) that efficiently form SOA. As NOx emissions decrease, the chemical regime of the atmosphere changes to one in which RO2 autoxidation becomes increasingly important, potentially increasing PM2.5, while oxidant availability driving RO2 formation rates simultaneously declines, possibly slowing regional PM2.5 formation. Using a suite of in situ aircraft observations and laboratory studies of HOM, together with a detailed molecular mechanism, we show that although autoxidation in an archetypal biogenic VOC system becomes more competitive as NOx decreases, absolute HOM production rates decrease due to oxidant reductions, leading to an overall positive coupling between anthropogenic NOx and localized biogenic SOA from autoxidation. This effect is observed in the Atlanta, Georgia, urban plume where HOM is enhanced in the presence of elevated NO, and predictions for Guangzhou, China, where increasing HOM-RO2 production coincides with increases in NO from 1990 to 2010. These results suggest added benefits to PM2.5 abatement strategies come with NOx emission reductions and have implications for aerosol-climate interactions due to changes in global SOA resulting from NOx interactions since the preindustrial era.

Observations of urban NOx plume dispersion using mobile and satellite DOAS measurements around the megacity of St.Petersburg (Russia)

ABSTRACTMobile DOAS (Differential Optical Absorption Spectroscopy) circular measurements of tropospheric nitrogen dioxide (NO2) were performed on a number of days in 2012 and 2014–2016 around St.Petersburg. These observations figured out an evolution of urban pollution plume, released from the megacity. The HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectories) model was configured to simulate the observed NO2 dispersion, taking into account the municipal inventory database of urban nitrogen oxides (NOx = NO+ NO2) emission. The simulation results were found consistent with the data of mobile measurements, allowing to fit an estimate of integral NOx emission rate from St.Petersburg (about 60 kt year−1 on the average). Coincident satellite measurements the Aura Ozone Monitoring Instrument (OMI) of tropospheric NO2 mostly agree with the data of simulation on the days of mobile observations. In general, presented results demonstrate the capabilities of joint interpretation of disparate tropospheric NO2 data in the vicinity of a megacity.

Characterizing the evolution of physical properties and mixing state of black carbon particles: from near a major highway to the broader urban plume in Los Angeles

Abstract. Black carbon (BC) particles can have deleterious human health consequences and impact regional and global climate. Uncertainties remain in part due to incomplete knowledge on the evolution of physical properties and mixing state of black carbon from sources to the remote atmosphere. We aim to understand how “road-to-ambient” processing and longer timescale aging in an urban plume affect black carbon physical properties. Refractory black carbon (rBC) was measured during summer 2016 using a single-particle soot photometer (SP2) in two distinct environments: near a major freeway and downwind of downtown Los Angeles. The near-road measurements were made at distances ranging from 30 to 114 m downwind of Interstate 405 in Los Angeles. These results were compared with measurements performed 100 km east of Los Angeles in Redlands, California. Coatings on rBC particles were quantified using two methods. As distance from the highway increased at the near-road site, we observed decreases in rBC mass and number concentrations and increases in the number fraction of rBC particles with thick coatings (f). The latter likely occurred due to rapid processing of the highway plume and entrainment of urban background particles. Most rBC-containing particles measured near the highway were either uncoated or thinly coated. In Redlands, we found that rBC mass concentrations on weekdays were similar to those observed at the furthest measured distance from the highway (114 m). However, rBC number concentrations for the smallest measured sizes were an order of magnitude lower in Redlands than all measured distances from the highway. Observations of f indicate that values in Redlands during periods when estimated photochemical age (PCA) was highest (6–8 h) were similar to corresponding values at the furthest measured distance from the highway. This suggests that the residence time of air in the Los Angeles Basin under typical summertime conditions measured during this campaign may not be sufficient for rBC to acquire thick coatings. However, under certain meteorological conditions, f was observed to be ∼0.20 in Redlands, with coating thickness histograms showing a larger contribution of rBC particles with coating thickness > 80 nm. This occurred during a weekend day when local emissions from diesel vehicles were lower (compared to weekdays) and winds brought air from the desert regions to Redlands, both of which would increase the relative contribution of remote sources of rBC. Afternoon values of f (and O3) were found to be systematically higher on weekends than weekdays, suggesting that the “weekend effect” can create more thickly coated rBC particles presumably due to enhanced secondary organic aerosol (SOA) and reduced available rBC as condensation sites.

Observations of Manaus urban plume evolution and interaction with biogenic emissions in GoAmazon 2014/5

As part of the Observations and Modeling of the Green Ocean Amazon (GoAmazon 2014/5) Experiment, detailed aerosol and trace gas measurements were conducted near Manaus, a metropolis located in the central Amazon Basin. Measurements of aerosol particles and trace gases were done downwind Manaus at the sites T2 (Tiwa Hotel) and T3 (Manacapuru), at a distance of 8 and 70 km from Manaus, respectively. Based on in-plume measurements closer to Manaus (site T2), the chemical signatures of city emissions were used to improve the interpretation of pollutant levels at the T3 site. We derived chemical and physical properties for the city's atmospheric emission ensemble, taking into account only air masses impacted by the Manaus plume at both sites, during the wet and dry season Intensive Operating Periods (IOPs). At T2, average concentrations of aerosol number (CN), CO and SO2 were 5500 cm−3 (between 10 and 490 nm), 145 ppb and 0.60 ppb, respectively, with a typical ratio ΔCN/ΔCO of 60–130 particles cm−3 ppb−1. The aerosol scattering (at RH < 60%) and absorption at 637 nm at T2 ranged from 10 to 50 M m−1 and 5–10 M m−1, respectively, leading to a mean single scattering albedo (SSA) of 0.70. In addition to identifying periods dominated by Manaus emissions at both T2 and T3, the plume transport between the two sampling sites was studied using back trajectory calculations. Results show that the presence of the Manaus plume at site T3 was important mainly during the daytime and at the end of the afternoons. During time periods directly impacted by Manaus emissions, an average aerosol number concentration of 3200 cm−3 was measured at T3. Analysis of plume evolution between T2 and T3 indicates a transport time of 4–5 h. Changes of submicron organic and sulfate aerosols ratios relative to CO (ΔOA/ΔCO and ΔSO4/ΔCO, respectively) indicate significant production of secondary organic aerosol (SOA), corresponding to a 40% mass increase in OA and a 30% in SO4 mass concentration. Similarly, during air mass arrival at T3 the SSA increased to 0.83 from 0.70 at T2, mainly associated with an increase in organic aerosol concentration. Aerosol particle size distributions show a strong decrease in the Aitken nuclei mode (10–100 nm) during the transport from T2 to T3, in particular above 30 nm, as a result of efficient coagulation processes into larger particles. A decrease of 30% in the particle number concentration and an increase of about 50 nm in geometric mean diameter were observed from T2 to T3 sites. The study of the evolution of aerosol properties downwind of the city of Manaus improves our understanding of how coupling of anthropogenic and biogenic sources may be impacting the sensitive Amazonian atmosphere.

Aircraft observations of the chemical composition and aging of aerosol in the Manaus urban plume during GoAmazon 2014/5

Abstract. The Green Ocean Amazon (GoAmazon 2014/5) campaign, conducted from January 2014 to December 2015 in the vicinity of Manaus, Brazil, was designed to study the aerosol life cycle and aerosol–cloud interactions in both pristine and anthropogenically influenced conditions. As part of this campaign, the U.S. Department of Energy (DOE) Gulfstream 1 (G-1) research aircraft was deployed from 17 February to 25 March 2014 (wet season) and 6 September to 5 October 2014 (dry season) to investigate aerosol and cloud properties aloft. Here, we present results from the G-1 deployments focusing on measurements of the aerosol chemical composition and secondary organic aerosol (SOA) formation and aging. In the first portion of the paper, we provide an overview of the data and compare and contrast the data from the wet and dry season. Organic aerosol (OA) dominates the deployment-averaged chemical composition, comprising 80 % of the non-refractory PM1 aerosol mass, with sulfate comprising 14 %, nitrate 2 %, and ammonium 4 %. This product distribution was unchanged between seasons, despite the fact that total aerosol loading was significantly higher in the dry season and that regional and local biomass burning was a significant source of OA mass in the dry, but not wet, season. However, the OA was more oxidized in the dry season, with the median of the mean carbon oxidation state increasing from −0.45 in the wet season to −0.02 in the dry season. In the second portion of the paper, we discuss the evolution of the Manaus plume, focusing on 13 March 2014, one of the exemplary days in the wet season. On this flight, we observe a clear increase in OA concentrations in the Manaus plume relative to the background. As the plume is transported downwind and ages, we observe dynamic changes in the OA. The mean carbon oxidation state of the OA increases from −0.6 to −0.45 during the 4–5 h of photochemical aging. Hydrocarbon-like organic aerosol (HOA) mass is lost, with ΔHOA∕ΔCO values decreasing from 17.6 µg m−3 ppmv−1 over Manaus to 10.6 µg m−3 ppmv−1 95 km downwind. Loss of HOA is balanced out by formation of oxygenated organic aerosol (OOA), with ΔOOA∕ΔCO increasing from 9.2 to 23.1 µg m−3 ppmv−1. Because hydrocarbon-like organic aerosol (HOA) loss is balanced by OOA formation, we observe little change in the net Δorg∕ΔCO values; Δorg∕ΔCO averages 31 µg m−3 ppmv−1 and does not increase with aging. Analysis of the Manaus plume evolution using data from two additional flights in the wet season showed similar trends in Δorg∕ΔCO to the 13 March flight; Δorg∕ΔCO values averaged 34 µg m−3 ppmv−1 and showed little change over 4–6.5 h of aging. Our observation of constant Δorg∕ΔCO are in contrast to literature studies of the outflow of several North American cities, which report significant increases in Δorg∕ΔCO for the first day of plume aging. These observations suggest that SOA formation in the Manaus plume occurs, at least in part, by a different mechanism than observed in urban outflow plumes in most other literature studies. Constant Δorg∕ΔCO with plume aging has been observed in many biomass burning plumes, but we are unaware of reports of fresh urban emissions aging in this manner. These observations show that urban pollution emitted from Manaus in the wet season forms less particulate downwind as it ages than urban pollution emitted from North American cities.

Tropospheric HONO distribution and chemistry in the southeastern US

Abstract. Here we report the measurement results of nitrous acid (HONO) and a suite of relevant parameters on the NCAR C-130 research aircraft in the southeastern US during the NOMADSS 2013 summer field study. The daytime HONO concentration ranged from low parts per trillion by volume (pptv) in the free troposphere (FT) to mostly within 5–15 pptv in the background planetary boundary layer (PBL). There was no discernible vertical HONO gradient above the lower flight altitude of 300 m in the PBL, and the transport of ground surface HONO was not found to be a significant contributor to the tropospheric HONO budget. The total in situ HONO source mean (±1 SD) was calculated as 53 (±21) pptv h−1 during the day. The upper-limit contribution from NOx-related reactions was 10 (±5) pptv h−1, and the contribution from photolysis of particulate nitrate (pNO3) was 38 (±23) pptv h−1, based on the measured pNO3 concentrations and the median pNO3 photolysis rate constant of 2.0 × 10−4 s−1 determined in the laboratory using ambient aerosol samples. The photolysis of HONO contributed to less than 10 % of the primary OH source. However, a recycling NOx source via pNO3 photolysis was equivalent to ∼ 2.3 × 10−6 mol m−2 h−1 in the air column within the PBL, a considerable supplementary NOx source in the low-NOx background area. Up to several tens of parts per trillion by volume of HONO were observed in power plant and urban plumes during the day, mostly produced in situ from precursors including NOx and pNO3. Finally, there was no observable accumulation of HONO in the nocturnal residual layer and the nocturnal FT in the background southeastern US, with an increase in the HONO ∕ NOx ratio of ≤ 3 × 10−4 h−1 after sunset.

Spatio-temporal patterns of high summer ozone events in the Madrid Basin, Central Spain

Complex spatial and temporal patterns of ground-level O3 and NO2 concentrations have been revealed across an important southern European O3 exceedance area (Madrid Basin, central Spain). Data were obtained from 102 diffusion tube sites and 49 monitoring stations (25 urban/suburban, 12 urban/suburban-traffic, 7 remote, 3 rural, 2 urban-industrial) located through a wide area inside and beyond the city. This new, high-density database confirms that current locations of monitoring stations in the Madrid networks are well positioned to record representative levels of O3 across the area. Two air quality monitoring stations were identified as reference measurement points, based on their lower O3 and NO2 concentrations, and used as a proxy for regional and hemispheric background levels. Although a main regional contribution was evidenced, emissions of local precursors within the Madrid urban plume play a key role in the generation of O3 exceedances, which are higher and occur earlier near the city than at rural sites, where the effect of NO titration is lower. Despite the fact that weekend emissions of O3 precursors in Madrid are typically lower than on weekdays, mainly due to fewer road traffic emissions, there is little difference in average values of weekday and weekend O3. However, more subtle “weekend effect” differences are revealed by probability density analysis, with high O3 and low NO2 at the highest temperature range (30-35° C) at weekends reflecting lower NO titration. This analysis highlights the importance of NO timing with respect to the photochemical activity timing. The complexity of these O3 pollution patterns in and around the city is dependent on an ever-changing interplay between weather conditions, emission sources, and the timescale required for pollutant transport, chemical processing and recirculation in an evolving contaminated airmass.