Urban Plume Research Articles

Long term measurements of the elemental composition and optical properties of aerosols in Amazonia

Aerosols are being collected and analyzed for trace elements in two sites in Amazonia since January 2008. On eof the site, Manaus is located in a very pristine area in Central Amazonia. The site is nt affected directly by any urban plume for thousands of kilometers. A second site is located in Porto Velho, in a region with heavy land use change and deforestation. Optical properties (light scattering ad absorption) are also being measured in order to study the climatic impact of aerosols. It was observed a clear seasonal pattern for both sites, with higher concentrations in the dry season. But the difference in seasonal concentrations observed for Porto Velho is much larger due to stronger anthropogenic influences. In Manaus during the wet season, very low concentrations of heavy metals, maybe the smallest measured in continental regions are reported. Positive Matrix Factorization (PMF) was used to separate the different aerosol components. In general, for fine and coarse mode and wet and dry season, 3 aerosol components could be observed: 1) Natural biogenic aerosol; 2) biomass burning component; 3) Soil dust both locally and long range transported Sahara dust

Impacts of black carbon mixing state on black carbon nucleation scavenging: Insights from a particle‐resolved model

This paper presents an advancement of the recently developed particle‐resolved aerosol model PartMC‐MOSAIC (Particle Monte Carlo‐Model for Simulating Aerosol Interactions and Chemistry) to investigate the impacts of mixing state on cloud droplet formation and to provide a tool for the quantification of errors in cloud properties introduced by simplifying mixing state assumptions. We coupled PartMC‐MOSAIC with a cloud parcel model. We initialized the cloud parcel simulation with hourly PartMC‐MOSAIC model output from a 48‐hour urban plume simulation. The cloud parcel model then explicitly simulated activation and condensational growth of the particles as the parcel underwent cooling at a specified rate and the particles of the aerosol population competed for water vapor. We used this capability to quantify the relative importance of size information versus composition information for the prediction of the cloud droplet number fraction, mass fraction of black carbon that is nucleation‐scavenged, cloud droplet effective radius, and relative dispersion of the droplet size distribution by introducing averaging of particle‐resolved information within prescribed bins. For the cloud droplet number fraction, both composition averaging and size‐bin averaging individually led to an error of less than 25% for all cloud parcel simulations, while averaging in both size bins and composition resulted in errors of up to 34% for the base case cooling rate of 0.5 K/min. In contrast, for the nucleation‐scavenged black carbon mass fraction, the results for size‐bin averaging tracked the reference case well, while composition averaging, with or without size‐bin averaging, led to overestimation of this quantity by up to 600%.

Characterization of submicron particles influenced by mixed biogenic and anthropogenic emissions using high-resolution aerosol mass spectrometry: results from CARES

Abstract. An Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during the Carbonaceous Aerosols and Radiative Effects Study (CARES) that took place in northern California in June 2010. We present results obtained at Cool (denoted as the T1 site of the project) in the foothills of the Sierra Nevada Mountains, where intense biogenic emissions are periodically mixed with urban outflow transported by daytime southwesterly winds from the Sacramento metropolitan area. During this study, the average mass loading of submicrometer particles (PM1) was 3.0 μg m−3, dominated by organics (80%) and sulfate (9.9%). The organic aerosol (OA) had a nominal formula of C1H1.38N0.004OM0.44, thus an average organic mass-to-carbon (OM/OC) ratio of 1.70. Two distinct oxygenated OA factors were identified via Positive matrix factorization (PMF) of the high-resolution mass spectra of organics. The more oxidized MO-OOA (O/C = 0.54) was interpreted as a surrogate for secondary OA (SOA) influenced by biogenic emissions whereas the less oxidized LO-OOA (O/C = 0.42) was found to represent SOA formed in photochemically processed urban emissions. LO-OOA correlated strongly with ozone and MO-OOA correlated well with two 1st generation isoprene oxidation products (methacrolein and methyl vinyl ketone), indicating that both SOAs were relatively fresh. A hydrocarbon like OA (HOA) factor was also identified, representing primary emissions mainly due to local traffic. On average, SOA (= MO-OOA + LO-OOA) accounted for 91% of the total OA mass and 72% of the PM1 mass observed at Cool. Twenty three periods of urban plumes from T0 (Sacramento) to T1 (Cool) were identified using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The average PM1 mass loading was considerably higher in urban plumes than in air masses dominated by biogenic SOA. The change in OA mass relative to CO (ΔOA/ΔCO) varied in the range of 5-196 μg m−3 ppm−1, reflecting large variability in SOA production. The highest ΔOA/ΔCO was reached when air masses were dominated by anthropogenic emissions in the presence of a high concentration of biogenic volatile organic compounds (BVOCs). This ratio, which was 97 μg m−3 ppm−1 on average, was much higher than when urban plumes arrived in a low BVOC environment (~36 μg m−3 ppm−1) or during other periods dominated by biogenic SOA (35 μg m−3 ppm−1). These results demonstrate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.

Overview of the 2010 Carbonaceous Aerosols and Radiative Effects Study (CARES)

Abstract. Substantial uncertainties still exist in the scientific understanding of the possible interactions between urban and natural (biogenic) emissions in the production and transformation of atmospheric aerosol and the resulting impact on climate change. The US Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) program's Carbonaceous Aerosol and Radiative Effects Study (CARES) carried out in June 2010 in Central Valley, California, was a comprehensive effort designed to improve this understanding. The primary objective of the field study was to investigate the evolution of secondary organic and black carbon aerosols and their climate-related properties in the Sacramento urban plume as it was routinely transported into the forested Sierra Nevada foothills area. Urban aerosols and trace gases experienced significant physical and chemical transformations as they mixed with the reactive biogenic hydrocarbons emitted from the forest. Two heavily-instrumented ground sites – one within the Sacramento urban area and another about 40 km to the northeast in the foothills area – were set up to characterize the evolution of meteorological variables, trace gases, aerosol precursors, aerosol size, composition, and climate-related properties in freshly polluted and "aged" urban air. On selected days, the DOE G-1 aircraft was deployed to make similar measurements upwind and across the evolving Sacramento plume in the morning and again in the afternoon. The NASA B-200 aircraft, carrying remote sensing instruments, was also deployed to characterize the vertical and horizontal distribution of aerosols and aerosol optical properties within and around the plume. This overview provides: (a) the scientific background and motivation for the study, (b) the operational and logistical information pertinent to the execution of the study, (c) an overview of key observations and initial findings from the aircraft and ground-based sampling platforms, and (d) a roadmap of planned data analyses and focused modeling efforts that will facilitate the integration of new knowledge into improved representations of key aerosol processes and properties in climate models.

Airborne measurements of trace gases and aerosols over the London metropolitan region

Abstract. The Emissions around the M25 motorway (EM25) campaign took place over the megacity of London in the United Kingdom in June 2009 with the aim of characterising trace gas and aerosol composition and properties entering and emitted from the urban region. It featured two mobile platforms, the UK BAe-146 Facility for Airborne Atmospheric Measurements (FAAM) research aircraft and a ground-based mobile lidar van, both travelling in circuits around London, roughly following the path of the M25 motorway circling the city. We present an overview of findings from the project, which took place during typical UK summertime pollution conditions. Emission ratios of volatile organic compounds (VOCs) to acetylene and carbon monoxide emitted from the London region were consistent with measurements in and downwind of other large urban areas and indicated traffic and associated fuel evaporation were major sources. Sub-micron aerosol composition was dominated by secondary species including sulphate (24% of sub-micron mass in the London plume and 29% in the non-plume regional aerosol), nitrate (24% plume; 20% regional) and organic aerosol (29% plume; 31% regional). The primary sub-micron aerosol emissions from London were minor compared to the larger regional background, with only limited increases in aerosol mass in the urban plume compared to the background (~12% mass increase on average). Black carbon mass was the major exception and more than doubled in the urban plume, leading to a decrease in the single scattering albedo from 0.91 in the regional aerosol to 0.86 in the London plume, on average. Our observations indicated that regional aerosol plays a major role on aerosol concentrations around London, at least during typical summertime conditions, meaning future efforts to reduce PM levels in London must account for regional as well as local aerosol sources.

Nitryl Chloride and Molecular Chlorine in the Coastal Marine Boundary Layer

The magnitude and sources of chlorine atoms in marine air remain highly uncertain but have potentially important consequences for air quality in polluted coastal regions. We made continuous measurements of ambient ClNO(2) and Cl(2) concentrations from May 15 to June 8 aboard the Research Vessel Atlantis during the CalNex 2010 field study. In the Los Angeles region, ClNO(2) was more ubiquitous than Cl(2) during most nights of the study period. ClNO(2) and Cl(2) ranged from detection limits at midday to campaign maximum values at night reaching 2100 and 200 pptv, respectively. The maxima were observed in Santa Monica Bay when sampling the Los Angeles urban plume. Cl(2) at times appeared well correlated with ClNO(2), but at other times, there was little to no correlation implying distinct and varying sources. Well-confined Cl(2) plumes were observed, largely independent of ClNO(2), providing support for localized industrial emissions of reactive chlorine. Observations of ClNO(2), Cl(2), and HCl are used to constrain a simple box model that predicts their relative importance as chlorine atom sources in the polluted marine boundary layer. In contrast to the emphasis in previous studies, ClNO(2) and HCl are dominant primary chlorine atom sources for the Los Angeles basin.

Aerosol effects on ozone concentrations in Beijing: A model sensitivity study

AbstractMost previous O3 simulations were based only on gaseous phase photochemistry. However, some aerosol-related processes, namely, heterogeneous reactions occurring on the aerosol surface and photolysis rate alternated by aerosol radiative influence, may affect O3 photochemistry under high aerosol loads. A three-dimensional air quality model, Models-3/Community Multi-scale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization, and Dissolution, was employed to simulate the effects of the above-mentioned processes on O3 formation under typical high O3 episodes in Beijing during summer. Five heterogeneous reactions, i.e., NO2, NO3, N2O5, HO2, and O3, were individually investigated to elucidate their effects on O3 formation. The results showed that the heterogeneous reactions significantly affected O3 formation in the urban plume. NO2 heterogeneous reaction increased O3 to 90 ppb, while HO2 heterogeneous reaction decreased O3 to 33 ppb. In addition, O3 heterogeneous loss decreased O3 to 31 ppb. The effects of NO2, NO3, and N2O5 heterogeneous reactions showed opposite O3 concentration changes between the urban and extra-urban areas because of the response of the reactions to the two types of O3 formation regimes. When the aerosol radiative influence was included, the photolysis rate decreased and O3 decreased significantly to 73 ppb O3. The two aerosol-related processes should be considered in the study of O3 formation because high aerosol concentration is a ubiquitous phenomenon that affects the urban- and regional air quality in China.

Impact of the Manaus urban plume on trace gas mixing ratios near the surface in the Amazon Basin: Implications for the NO‐NO2‐O3 photostationary state and peroxy radical levels

We measured the mixing ratios of NO, NO2, O3, and volatile organic carbon as well as the aerosol light‐scattering coefficient on a boat platform cruising on rivers downwind of the city of Manaus (Amazonas State, Brazil) in July 2001 (Large‐Scale Biosphere‐Atmosphere Experiment in Amazonia‐Cooperative LBA Airborne Regional Experiment‐2001). The dispersion and impact of the Manaus plume was investigated by a combined analysis of ground‐based (boat platform) and airborne trace gas and aerosol measurements as well as by meteorological measurements complemented by dispersion calculations (Hybrid Single‐Particle Lagrangian Integrated Trajectory model). For the cases with the least anthropogenic influence (including a location in a so far unexplored region ∼150 km west of Manaus on the Rio Manacapuru), the aerosol scattering coefficient, σs, was below 11 Mm−1, NOx mixing ratios remained below 0.6 ppb, daytime O3 mixing ratios were mostly below 20 ppb and maximal isoprene mixing ratios were about 3 ppb in the afternoon. The photostationary state (PSS) was not established for these cases, as indicated by values of the Leighton ratio, Φ, well above unity. Due to the influence of river breeze systems and other thermally driven mesoscale circulations, a change of the synoptic wind direction from east‐northeast to south‐southeast in the afternoon often caused a substantial increase of σs and trace gas mixing ratios (about threefold for σs, fivefold for NOx, and twofold for O3), which was associated with the arrival of the Manaus pollution plume at the boat location. The ratio Φ reached unity within its uncertainty range at NOx mixing ratios of about 3 ppb, indicating “steady‐state” conditions in cases when radiation variations, dry deposition, emissions, and reactions mostly involving peroxy radicals (XO2) played a minor role. The median midday/afternoon XO2 mixing ratios estimated using the PSS method range from 90 to 120 parts per trillion (ppt) for the remote cases (σs < 11 Mm−1 and NOx < 0.6 ppb), while for the polluted cases our estimates are 15 to 60 ppt. These values are within the range of XO2 estimated by an atmospheric chemistry box model (Chemistry As A Box model Application‐Module Efficiently Calculating the Chemistry of the Atmosphere (CAABA/MECCA)‐3.0).

Emission sources sensitivity study for ground-level ozone and PM2.5 due to oil sands development using air quality modelling system: Part II – Source apportionment modelling

We conducted four source apportionment simulations using the Community Multiscale Air Quality (CMAQ) photochemical grid modelling system in order to investigate and assess the relative importance of specific emissions sources and/or geographic regions on ambient ozone and PM air quality in the Alberta Oil Sands Region (AOSR). Local point and area sources, medium range transport of mobile sources and biogenic emissions were examined.The elimination of emissions from local stationary point sources reduced 8-h ozone concentrations and greatly reduces the PM2.5 concentrations in AOSR; similar results are seen in the local area source zero-out simulations but with less ozone and PM2.5 reductions than seen in the local point source zero-out run. Although the mobile source medium-range transport reduced 8-h ozone concentrations in the urban plume from Edmonton that results in some ozone and PM2.5 concentration reductions in the southern part of the AOSR, it has little effect on the elevated ozone and PM2.5 concentrations in the oil sands development area of the AOSR where the highest ozone and PM2.5 concentrations are estimated. The elimination of all anthropogenic emissions in Alberta so that only biogenic emissions remained resulted in large reductions in 8-h ozone concentrations in the AOSR, with the highest remaining ozone in the 50–52ppb range occurring south of Fort McMurray; very low PM2.5 concentrations are also estimated across Alberta, including the AOSR, when anthropogenic emissions are eliminated in Alberta.

Analysis and fit of surface CO2 concentrations at a rural site

The impact of CO(2) urban plume in a rural area was investigated by concentrations recorded near surface. CO(2) dry concentrations at three levels near surface were recorded for about 8months at a rural site. Daily cycles were obtained and directional analysis was made with percentiles. Several functions were used to fit background and plume concentrations and the goodness of fit was evaluated with different statistics, which were also compared. Daily cycle showed a difference of around 2ppm during the night between the lowest (1.8m) and the highest (8.3m) levels. Weighting functions of the directional analysis revealed the influence of the Valladolid urban plume. Two regions were established, with local factors prevailing below 3m s(-1) and transport dominating above 6m s(-1). The best fit was achieved with a quadratic function for the background and a cubic function for the plume due to the lack of symmetry observed. Gamma and Weibull distributions were also successfully used. Some statistics, such as the root mean square error (RMSE), stood out when evaluating the goodness of fit, whilst others were discarded due to their extremely low values and the lack of sensitivity against the functions used. Finally, a comprehensive metric merging several statistics was also tested with slight differences against RMSE.

Impact of the regional transport of urban Beijing pollutants on downwind areas in summer: ozone production efficiency analysis

ABSTRACTAmbient measurements of SO2, O3, NOx, NOy and CO were made at Shangdianzi (SDZ), a rural site in the northeast (NE) of Beijing, and urban Beijing (China Meteorological Administration) from 1 June 2008 to 31 August 2008. The pollutants at SDZ showed very different levels under different wind conditions, with the levels under the southwest (SW) wind being much higher than those under the NE wind. The SW wind facilitates the transport of urban plume to SDZ, whereas the NE wind provides a background condition. At SDZ, the Ozone (O3) concentration in air masses from urban Beijing was found to be 33.4 ± 0.4 ppbv higher than that from clean regions in summer. The ozone production efficiency (OPEx) for the urban plume and background condition was 4.0 and 5.3, respectively. Based on these OPEx values and the NOz values for the respective conditions, the contribution of in-situ production in the urban plume to the level of O3 at SDZ is estimated to be 8.6 ppbv, corresponding only to 25.7% of the total impact of urban plume transport. This suggests that direct transport of O3 rather than in-situ photochemistry contributes mainly to the summer elevation of the level of O3 at SDZ.

Measurements of ozone and its precursors in Beijing during summertime: impact of urban plumes on ozone pollution in downwind rural areas

Abstract. Sea-land and mount-valley circulations are the dominant mesoscale synoptic systems affecting the Beijing area during summertime. Under the influence of these two circulations, the prevailing wind is southwesterly from afternoon to midnight, and then changes to northeasterly till forenoon. In this study, surface ozone (O3), carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO2), nitrogen oxide (NOx) and non-methane hydrocarbons (NMHCs) were measured at four sites located along the route of prevailing wind, including two upwind urban sites (Fengtai "FT" and Baolian "BL"), an upwind suburban site (Shunyi "SY") and a downwind rural site (Shangdianzi "SDZ") during 20 June–16 September 2007. The purpose is to improve our understanding of ozone photochemistry in urban and rural areas of Beijing and the influence of urban plumes on ozone pollution in downwind rural areas. It is found that ozone pollution was synchronism in the urban and rural areas of Beijing, coinciding with the regional-scale synoptic processes. Due to the high traffic density and local emissions, the average levels of reactive gases NOx and NMHCs at the non-rural sites were much higher than those at SDZ. The level of long-lived gas CO at SDZ was comparable to, though slightly lower than, at the urban sites. We estimate the photochemical reactivity (LOH and the ozone formation potential (OFP) in the urban (BL) and rural (SDZ) areas using measured CO and NMHCs. The OH loss rate coefficient (LOH by total NMHCs at the BL and SDZ sites are estimated to be 50.7 s-1 and 15.8 s-1, respectively. While alkenes make a major contribution to the LOH, aromatics dominate OFP at both urban and rural sites. With respect to the individual species, CO has the largest ozone formation potential at the rural site, and at the urban site aromatic species are the leading contributors. While the O3 diurnal variations at the four sites are typical for polluted areas, the ozone peak values are found to lag behind one site after another along the route of prevailing wind from SW to NE. Intersection analyses of trace gases reveal that polluted air masses arriving at SDZ were more aged with both higher O3 and Ox concentrations than those at BL. The results indicate that urban plume can transport not only O3 but its precursors, the latter leading more photochemical O3 production when being mixed with background atmosphere in the downwind rural area.

Rural Southeast Texas Air Quality Measurements during the 2006 Texas Air Quality Study

ABSTRACT The authors conducted air quality measurements of the criteria pollutants carbon monoxide, nitrogen oxides, and ozone together with meteorological measurements at a park site southeast of College Station, TX, during the 2006 Texas Air Quality Study II (TexAQS). Ozone, a primary focus of the measurements, was above 80 ppb during 3 days and above 75 ppb during additional 8 days in summer 2006, suggestive of possible violations of the ozone National Ambient Air Quality Standard (NAAQS) in this area. In concordance with other air quality measurements during the TexAQS II, elevated ozone mixing ratios coincided with northerly flows during days after cold front passages. Ozone background during these days was as high as 80 ppb, whereas southerly air flows generally provided for an ozone background lower than 40 ppb. Back trajectory analysis shows that local ozone mixing ratios can also be strongly affected by the Houston urban pollution plume, leading to late afternoon ozone increases of as high as 50 ppb above background under favorable transport conditions. The trajectory analysis also shows that ozone background increases steadily the longer a southern air mass resides over Texas after entering from the Gulf of Mexico. In light of these and other TexAQS findings, it appears that ozone air quality is affected throughout east Texas by both long-range and regional ozone transport, and that improvements therefore will require at least a regionally oriented instead of the current locally oriented ozone precursor reduction policies. IMPLICATIONS Ozone National Ambient Air Quality Standard (NAAQS) violations in the two major Texas metropolitan areas have been occurring for decades. Recent data show that high ozone concentrations in east Texas are not limited to the Houston and Dallas/Fort Worth areas, but can be transported far downwind, possibly leading to NAAQS violations in rural areas. This paper provides an assessment of rural ozone concentrations in Brazos County, 120 km northwest of Houston during summer 2006, showing that this area likely violated the NAAQS, in part due to long-range transport importing high ozone background concentrations, in part due to impacts of the Houston pollution plume under southeast wind directions.

Variations in time and space of trace metal aerosol concentrations in urban areas and their surroundings

Abstract. Using an unprecedentedly large geochemical database, we compare temporal and spatial variations in inhalable trace metal background concentrations in a major city (Barcelona, Spain) and at a nearby mountainous site (Montseny) affected by the urban plume. Both sites are contaminated by technogenic metals, with V, Pb, Cu, Zn, Mn, Sn, Bi, Sb and Cd all showing upper continental crust (UCC) normalised values >1 in broadly increasing order. The highest metal concentrations usually occur during winter at Barcelona and summer in Montseny. This seasonal difference was especially marked at the remote mountain site in several elements such as Ti and Rare Earth Elements, which recorded campaign maxima, exceeding PM10 concentrations seen in Barcelona. The most common metals were Zn, Ti, Cu, Mn, Pb and V. Both V and Ni show highest concentrations in summer, and preferentially fractionate into the finest PM sizes (PM1/PM10 > 0.5) especially in Barcelona, this being attributed to regionally dispersed contamination from fuel oil combustion point sources. Within the city, hourly metal concentrations are controlled either by traffic (rush hour double peak for Cu, Sb, Sn, Ba) or industrial plumes (morning peak of Ni, Mn, Cr generated outside the city overnight), whereas at Montseny metal concentrations rise during the morning to a single, prolonged afternoon peak as contaminated air transported by the sea breeze moves into the mountains. Our exceptional database, which includes hourly measurements of chemical concentrations, demonstrates in more detail than previous studies the spatial and temporal variability of urban pollution by trace metals in a given city. Technogenic metalliferous aerosols are commonly fine in size and therefore potentially bioavailable, emphasising the case for basing urban background PM characterisation not only on physical parameters such as mass but also on sample chemistry and with special emphasis on trace metal content.

Phytoscreening for Chlorinated Solvents Using Rapid in Vitro SPME Sampling: Application to Urban Plume in Verl, Germany

Rapid detection and delineation of contaminants in urban settings is critically important in protecting human health. Cores from trees growing above a plume of contaminated groundwater in Verl, Germany, were collected in 1 day, with subsequent analysis and plume mapping completed over several days. Solid-phase microextraction (SPME) analysis was applied to detect tetrachloroethene (PCE) and trichloroethene (TCE) to below nanogram/liter levels in the transpiration stream of the trees. The tree core concentrations showed a clear areal correlation to the distribution of PCE and TCE in the groundwater. Concentrations in tree cores were lower than the underlying groundwater, as anticipated; however, the tree core water retained the PCE:TCE signature of the underlying groundwater in the urban, populated area. The PCE:TCE ratio can indicate areas of differing degradation activity. Therefore, the phytoscreening analysis was capable not only of mapping the spatial distribution of groundwater contamination but also of delineating zones of potentially differing contaminant sources and degradation. The simplicity of tree coring and the ability to collect a large number of samples in a day with minimal disruption or property damage in the urban setting demonstrates that phytoscreening can be a powerful tool for gaining reconnaissance-level information on groundwater contaminated by chlorinated solvents. The use of SPME decreases the detection level considerably and increases the sensitivity of phytoscreening as an assessment, monitoring, and phytoforensic tool. With rapid, inexpensive, and noninvasive methods of detecting and delineating contaminants underlying homes, as in this case, human health can be better protected through screening of broader areas and with far faster response times.

Black carbon aerosol mixing state, organic aerosols and aerosol optical properties over the United Kingdom

Abstract. Black carbon (BC) aerosols absorb sunlight thereby leading to a positive radiative forcing and a warming of climate and can also impact human health through their impact on the respiratory system. The state of mixing of BC with other aerosol species, particularly the degree of internal/external mixing, has been highlighted as a major uncertainty in assessing its radiative forcing and hence its climate impact, but few in situ observations of mixing state exist. We present airborne single particle soot photometer (SP2) measurements of refractory BC (rBC) mass concentrations and mixing state coupled with aerosol composition and optical properties measured in urban plumes and regional pollution over the United Kingdom. All data were obtained using instrumentation flown on the UK's BAe-146-301 large Atmospheric Research Aircraft (ARA) operated by the Facility for Airborne Atmospheric Measurements (FAAM). We measured sub-micron aerosol composition using an aerosol mass spectrometer (AMS) and used positive matrix factorization to separate hydrocarbon-like (HOA) and oxygenated organic aerosols (OOA). We found a higher number fraction of thickly coated rBC particles in air masses with large OOA relative to HOA, higher ozone-to-nitrogen oxides (NOx) ratios and large concentrations of total sub-micron aerosol mass relative to rBC mass concentrations. The more ozone- and OOA-rich air masses were associated with transport from continental Europe, while plumes from UK cities had higher HOA and NOx and fewer thickly coated rBC particles. We did not observe any significant change in the rBC mass absorption efficiency calculated from rBC mass and light absorption coefficients measured by a particle soot absorption photometer despite observing significant changes in aerosol composition and rBC mixing state. The contributions of light scattering and absorption to total extinction (quantified by the single scattering albedo; SSA) did change for different air masses, with lower SSA observed in urban plumes compared to regional aerosol (0.85 versus 0.9–0.95). We attribute these differences to the presence of relatively rapidly formed secondary aerosol, primarily OOA and ammonium nitrate, which must be taken into account in radiative forcing calculations.

Weighted Flow Algorithms (WFA) for stochastic particle coagulation

Stochastic particle-resolved methods are a useful way to compute the time evolution of the multi-dimensional size distribution of atmospheric aerosol particles. An effective approach to improve the efficiency of such models is the use of weighted computational particles. Here we introduce particle weighting functions that are power laws in particle size to the recently-developed particle-resolved model PartMC-MOSAIC and present the mathematical formalism of these Weighted Flow Algorithms (WFA) for particle coagulation and growth. We apply this to an urban plume scenario that simulates a particle population undergoing emission of different particle types, dilution, coagulation and aerosol chemistry along a Lagrangian trajectory. We quantify the performance of the Weighted Flow Algorithm for number and mass-based quantities of relevance for atmospheric sciences applications.

Differences between carbon dioxide levels over suburban and rural sites in Northern Spain

A comparison between suburban and rural atmospheric carbon dioxide concentrations in Northern Spain is made. Measurements were carried out from April 2006 to November 2007 using MIR 9000 continuous analyzers based on the infrared technique. Two locations were established: a suburban site in Valladolid, a medium-sized city, and a rural location at CIBA, approximately 24 km northwest of Valladolid. Mean suburban CO(2) concentrations are 4.5 ppm higher than rural levels. Frequencies of suburban concentrations from 400 to 450 ppm were around twice the rural frequencies. The suburban daily evolution presented two maxima in the predawn hours and at 1900-2000 GMT, mainly associated to anthropogenic emissions which also affected maximum concentrations recorded in autumn-winter and minimum levels in summer. The rural variation with minimum values during the day and high levels at night is mainly related to vegetation activity which also impacts the highest CO(2) concentrations obtained in spring, coinciding with maximum vegetation growth. Boundary layer processes also affected variability of concentrations recorded at both sites. Air quality at the rural site was also influenced by air mass transport from the urban plume (S, SSE, and ESE), which had a mean CO(2) value of 402 ppm. By contrast, concentrations were low when SW-W and NW winds prevailed and brought cleaner air. The relationship between rural CO(2) concentrations and wind speed using a mathematical fit provides a valuable estimation of the background level at the site, 384.8 ppm.

Modeling ozone plumes observed downwind of New York City over the North Atlantic Ocean during the ICARTT field campaign

Abstract. Transport and chemical transformation of well-defined New York City (NYC) urban plumes over the North Atlantic Ocean were studied using aircraft measurements collected on 20–21 July 2004 during the ICARTT (International Consortium for Atmospheric Research on Transport and Transformation) field campaign and WRF-Chem (Weather Research and Forecasting-Chemistry) model simulations. The strong NYC urban plumes were characterized by carbon monoxide (CO) mixing ratios of 350–400 parts per billion by volume (ppbv) and ozone (O3) levels of about 100 ppbv near New York City on 20 July in the WP-3D in-situ and DC-3 lidar aircraft measurements. On 21 July, the two aircraft captured strong urban plumes with about 350 ppbv CO and over 150 ppbv O3 (~160 ppbv maximum) about 600 km downwind of NYC over the North Atlantic Ocean. The measured urban plumes extended vertically up to about 2 km near New York City, but shrank to 1–1.5 km over the stable marine boundary layer (MBL) over the North Atlantic Ocean. The WRF-Chem model reproduced ozone formation processes, chemical characteristics, and meteorology of the measured urban plumes near New York City (20 July) and in the far downwind region over the North Atlantic Ocean (21 July). The quasi-Lagrangian analysis of transport and chemical transformation of the simulated NYC urban plumes using WRF-Chem results showed that the pollutants can be efficiently transported in (isentropic) layers in the lower atmosphere (<2–3 km) over the North Atlantic Ocean while maintaining a dynamic vertical decoupling by cessation of turbulence in the stable MBL. The O3 mixing ratio in the NYC urban plumes remained at 80–90 ppbv during nocturnal transport over the stable MBL, then grew to over 100 ppbv by daytime oxidation of nitrogen oxides (NOx = NO + NO2) with mixing ratios on the order of 1 ppbv. Efficient transport of reactive nitrogen species (NOy), specifically nitric acid (HNO3), was confirmed through the comparison of the CO/NOy ratio in photochemically fresh and aged NYC plumes, implying the possibility of long-range transport of O3 over the stable MBL over the North Atlantic Ocean in association with NOx regeneration mechanism. The impact of chemical initial and boundary conditions (IC/BCs) on modelled O3 urban plumes was investigated in terms of the background O3 level and the vertical structure of the urban plumes. Simulations with dynamic ("time-variant") chemical IC/BCs enhanced the O3 level by 2–12 ppbv on average in the atmospheric layer below 3 km, showing better agreement with the observed NYC plumes and biomass-burning plumes than the simulation with prescribed static IC/BCs. The simulation including MOZART-4 chemical IC/BCs and Alaskan/Canadian wildfire emissions compared better to the observed O3 profiles in the upper atmospheric layer (>~3 km) than models that only accounted for North American anthropogenic/biogenic and wildfire contributions to background ozone. The comparison between models and observations show that chemical IC/BCs must be properly specified to achieve accurate model results.

Emissions and photochemistry of oxygenated VOCs in urban plumes in the Northeastern United States

Abstract. Photochemical processes inside urban plumes in the Northeast of the United States have been studied using a highly detailed chemical model, based upon the Master Chemical Mechanism (MCM). The model results have been compared to measurements of oxygenated VOCs (acetone, methyl ethyl ketone, acetaldehyde, acetic acid and methanol) obtained during several flights of the NOAA WP-3D aircraft, which sampled plumes from the New York City area during the ICARTT campaign in 2004. The agreement between the model and the measurements was within 40–60 % for all species, except acetic acid. The model results have been used to study the formation and photochemical evolution of acetone, methyl ethyl ketone and acetaldehyde. Under the conditions encountered during the ICARTT campaign, acetone is produced from the oxidation of propane (24–28 %) and i-propanol (<15 %) and from a number of products of i-pentane oxidation. Methyl ethyl ketone (MEK) is mostly produced from the oxidation of n-butane (20–30 %) and 3-methylpentane (<40 %). Acetaldehyde is formed from several precursors, mostly small alkenes, >C5 alkanes, propanal and MEK. Ethane and ethanol oxidation account, respectively, for 6–23 % and 5–25 % of acetaldehyde photochemical formation. The results highlight the importance of alkanes for the photochemical production of ketones and the role of hydroperoxides in sustaining their formation far from the emission sources.