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Air pollution in urban environments has been shown to have a negative impact on air quality and human health, particularly in megacities. Over recent decades, Delhi, India, has suffered high atmospheric pollution, with significant particulate matter (PM) concentrations as a result of anthropogenic activities. Organic aerosols (OAs) are composed of thousands of different chemical species and are one of the main constituents of submicron particles. However, quantitative knowledge of OA composition, their sources and their processes in urban environments is still limited. This is important particularly in India, as Delhi is a massive, inhomogeneous conurbation, where we would expect the apportionment and concentrations to vary depending on where in Delhi the measurements/source apportionment is performed, indicating the need for multisite measurements. This study presents the first multisite analysis carried out in India over different seasons, with a focus on identifying OA sources. The measurements were taken during 2018 at two sites in Delhi, India. One site was located at the India Meteorological Department, New Delhi (ND). The other site was located at the Indira Gandhi Delhi Technical University for Women, Old Delhi (OD). Non-refractory submicron aerosol (NR-PM1) concentrations (ammonium, nitrate, sulfate, chloride and organic aerosols) of four aerosol mass spectrometers were analysed. Collocated measurements of volatile organic compounds, black carbon, NOx and CO were performed. Positive matrix factorisation (PMF) analysis was performed to separate the organic fraction, identifying a number of conventional factors: hydrocarbon-like OAs (HOAs) related to traffic emissions, biomass burning OAs (BBOAs), cooking OAs (COAs) and secondary OAs (SOAs). A composition-based estimate of PM1 is defined by combining black carbon (BC) and NR-PM1 (C-PM1= BC + NR-PM1). No significant difference was observed in C-PM1 concentrations between sites, OD (142 ± 117 µg m−3) compared to ND (123 ± 71 µg m3), from post-monsoon measurements. A wider variability was observed between seasons, where pre-monsoon and monsoon showed C-PM1 concentrations lower than 60 µg m−3. A seasonal variation in C-PM1 composition was observed; SO42- showed a high contribution over pre-monsoon and monsoon seasons, while NO3- and Cl− had a higher contribution in winter and post-monsoon. The main primary aerosol source was from traffic, which is consistent with the PMF analysis and Aethalometer model analysis. Thus, in order to reduce PM1 concentrations in Delhi through local emission controls, traffic emission control offers the greatest opportunity. PMF–aerosol mass spectrometer (AMS) mass spectra will help to improve future aerosol source apportionment studies. The information generated in this study increases our understanding of PM1 composition and OA sources in Delhi, India. Furthermore, the scientific findings provide significant information to strengthen legislation that aims to improve air quality in India.

Local and regional modelling of NH3 surface exchange is required to quantify nitrogen deposition to, and emissions from, the biosphere. However, measurements and model parameterisations for many remote ecosystems – such as tropical rainforest – remain sparse. Using 1 month of hourly measurements of NH3 fluxes and meteorological parameters over a remote Amazon rainforest site (Amazon Tall Tower Observatory, ATTO), six model parameterisations based on a bidirectional, single-layer canopy compensation point resistance model were developed to simulate observations of NH3 surface exchange. Canopy resistance was linked to either relative humidity at the canopy level (RHz0′), vapour pressure deficit, or a parameter value based on leaf wetness measurements. The ratio of apoplastic NH4+ to H+ concentration, Γs, during this campaign was inferred to be 38.5 ± 15.8. The parameterisation that reproduced the observed net exchange of NH3 most accurately was the model that used a cuticular resistance (Rw) parameterisation based on leaf wetness measurements and a value of Γs=50 (Pearson correlation r=0.71). Conversely, the model that performed the worst at replicating measured NH3 fluxes used an Rw value modelled using RHz0′ and the inferred value of Γs=38.5 (r=0.45). The results indicate that a single-layer canopy compensation point model is appropriate for simulating NH3 fluxes from tropical rainforest during the Amazonian dry season and confirmed that a direct measurement of (a non-binary) leaf wetness parameter improves the ability to estimate Rw. Current inferential methods for determining Γs were noted as having difficulties in the humid conditions present at a rainforest site.

The Amazon rainforest presents a unique, natural laboratory for the study of surface–atmosphere interactions. Its alternation between a near-pristine marine-influenced atmosphere during the wet season and a vulnerable system affected by periodic intrusions of anthropogenic pollution during the dry season provides an opportunity to investigate some fundamental aspects of boundary-layer chemical processes. This study presents the first simultaneous hourly measurements of concentrations, fluxes, and deposition velocities of the inorganic trace gases NH3, HCl, HONO, HNO3, and SO2 as well as their water-soluble aerosol counterparts NH4+, Cl−, NO2-, NO3- and SO42- over the Amazon. Species concentrations were measured in the dry season (from 6 October to 5 November 2017), at the Amazon Tall Tower Observatory (ATTO) in Brazil, using a two-point gradient wet-chemistry instrument (GRadient of AErosols and Gases Online Registration, GRAEGOR) sampling at 42 and 60 m. Fluxes and deposition velocities were derived from the concentration gradients using a modified form of the aerodynamic gradient method corrected for measurement within the roughness sub-layer. Findings from this campaign include observations of elevated concentrations of NH3 and SO2 partially driven by long-range transport (LRT) episodes of pollution and the substantial influence of coarse Cl− and NO3- particulate on overall aerosol mass burdens. From the flux measurements, the dry season budget of total reactive nitrogen dry deposition at the ATTO site was estimated as −2.9 kg N ha-1a-1. HNO3 and HCl were deposited continuously at a rate close to the aerodynamic limit. SO2 was deposited with an average daytime surface resistance (Rc) of 28 s m−1, whilst aerosol components showed average surface deposition velocities of 2.8 and 2.7 mm s−1 for SO42- and NH4+, respectively. Deposition rates of NO3- and Cl− were higher at 7.1 and 7.8 mm s−1, respectively, reflecting their larger average size. The exchange of NH3 and HONO was bidirectional, with NH3 showing emission episodes in the afternoon and HONO in the early morning hours. This work provides a unique dataset to test and improve dry deposition schemes for these compounds for tropical rainforest, which have typically been developed by interpolation from conditions in temperate environments. A future campaign should focus on making similar measurements in the wet season in order to provide a complete view of the annual pattern of inorganic trace gas and coarse aerosol biosphere–atmosphere exchange over tropical rainforest.

The increasing use of intensive agricultural practices can lead to damaging consequences for the atmosphere through enhanced emissions of air pollutants. However, there are few direct measurements of the surface–atmosphere exchange of trace gases and water-soluble aerosols over agricultural grassland, particularly of reactive nitrogen compounds. In this study, we present measurements of the concentrations, fluxes and deposition velocities of the trace gases HCl, HONO, HNO3, SO2 and NH3 as well as their associated water-soluble aerosol counterparts Cl−, NO2−, NO3−, SO42− and NH4+ as determined hourly for 1 month in May–June 2016 over agricultural grassland near Edinburgh, UK, pre- and postfertilisation. Measurements were made using the Gradient of Aerosols and Gases Online Registrator (GRAEGOR) wet-chemistry two-point gradient instrument. Emissions of NH3 peaked at 1460 ng m−2 s−1 3 h after fertilisation, with an emission of HONO peaking at 4.92 ng m−2 s−1 occurring 5 h after fertilisation. Apparent emissions of NO3− aerosol were observed after fertilisation which, coupled with a divergence of HNO3 deposition velocity (Vd) from its theoretical maximum value, suggested the reaction of emitted NH3 with atmospheric HNO3 to form ammonium nitrate aerosol. The use of the conservative exchange fluxes of tot-NH4+ and tot-NO3− indicated net emission of tot-NO3−, implying a ground source of HNO3 after fertilisation. Daytime concentrations of HONO remained above the detection limit (30 ng m−3) throughout the campaign, suggesting a daytime source for HONO at the site. Whilst the mean Vd of NH4+ was 0.93 mm s−1 in the range expected for the accumulation mode, the larger average Vd for Cl− (3.65 mm s−1), NO3− (1.97 mm s−1) and SO42− (1.89 mm s−1) reflected the contribution of a super-micron fraction and decreased with increasing PM2.5∕PM10 ratio (a proxy measurement for aerosol size), providing evidence – although limited by the use of a proxy for aerosol size – of a size dependence of aerosol deposition velocity for aerosol chemical compounds, which has been suggested from process-orientated models of aerosol deposition.

Studying the vertical distribution of aerosol particle physical and chemical properties in the troposphere is essential to understand the relative importance of local emission processes vs. long-range transport for column-integrated aerosol properties (e.g. the aerosol optical depth, AOD, affecting regional climate) as well as for the aerosol burden and its impacts on air quality at the ground. The main objective of this paper is to investigate the transport of desert dust in the middle troposphere and its intrusion into the planetary boundary layer (PBL) over the Po Valley (Italy), a region considered one of the greatest European pollution hotspots for the frequency that particulate matter (PM) limit values are exceeded. Events of mineral aerosol uplift from local (soil) sources and phenomena of hygroscopic growth at the ground are also investigated, possibly affecting the PM concentration in the region as well. During the PEGASOS 2012 field campaign, an integrated observing–modelling system was set up based on near-surface measurements (particle concentration and chemistry), vertical profiling (backscatter coefficient profiles from lidar and radiosoundings) and Lagrangian air mass transport simulations by FLEXPART model. Measurements were taken at the San Pietro Capofiume supersite (44°39′ N, 11°37′ E; 11 m a.s.l.), located in a rural area relatively close to some major urban and industrial emissive areas in the Po Valley. Mt. Cimone (44°12′ N, 10°42′ E; 2165 m a.s.l.) WMO/GAW station observations are also included in the study to characterize regional-scale variability. Results show that, in the Po Valley, aerosol is detected mainly below 2000 m a.s.l. with a prevalent occurrence of non-depolarizing particles ( > 50 % throughout the campaign) and a vertical distribution modulated by the PBL daily evolution. Two intense events of mineral dust transport from northern Africa (19–21 and 29 June to 2 July) are observed, with layers advected mainly above 2000 m, but subsequently sinking and mixing in the PBL. As a consequence, a non-negligible occurrence of mineral dust is observed close to the ground ( ∼ 7 % of occurrence during a 1-month campaign). The observations unambiguously show Saharan dust layers intruding the Po Valley mixing layer and directly affecting the aerosol concentrations near the surface. Finally, lidar observations also indicate strong variability in aerosol on shorter timescales (hourly). Firstly, these highlight events of hygroscopic growth of anthropogenic aerosol, visible as shallow layers of low depolarization near the ground. Such events are identified during early morning hours at high relative humidity (RH) conditions (RH > 80 %). The process is observed concurrently with high PM1 nitrate concentration (up to 15 µg cm−3) and hence mainly explicable by deliquescence of fine anthropogenic particles, and during mineral dust intrusion episodes, when water condensation on dust particles could instead represent the dominant contribution. Secondly, lidar images show frequent events (mean daily occurrence of ∼ 22 % during the whole campaign) of rapid uplift of mineral depolarizing particles in afternoon–evening hours up to 2000 m a.s.l. height. The origin of such particles cannot be directly related to long-range transport events, being instead likely linked to processes of soil particle resuspension from agricultural lands.

There is limited availability of long-term, high temporal resolution, chemically speciated aerosol measurements which can provide further insight into the health and environmental impacts of particulate matter. The Monitor for AeRosols and Gases (MARGA, Applikon B.V., NL) allows for the characterisation of the inorganic components of PM10 and PM2.5 (NH4+, NO3-, SO42-, Cl-, Na+, K+, Ca2+, Mg2+) and inorganic reactive gases (NH3, SO2, HCl, HONO and HNO3) at hourly resolution. The following study presents 6.5 years (June 2006 to December 2012) of quasi-continuous observations of PM2.5 and PM10 using the MARGA at the UK EMEP supersite, Auchencorth Moss, SE Scotland. Auchencorth Moss was found to be representative of a remote European site with average total water soluble inorganic mass of PM2.5 of 3.82 μg m−3. Anthropogenically derived secondary inorganic aerosols (sum of NH4+, NO3- and nss-SO42−) were the dominating species (63 %) of PM2.5. In terms of equivalent concentrations, NH4+ provided the single largest contribution to PM2.5 fraction in all seasons. Sea salt was the main component (73 %) of the PMcoarse fraction (PM10-PM2.5), though NO3- was also found to make a relatively large contribution to the measured mass (17 %) providing evidence of considerable processing of sea salt in the coarse mode. There was on occasions evidence of aerosol from combustion events being transported to the site in 2012 as high K+ concentrations (deviating from the known ratio in sea salt) coincided with increases in black carbon at the site. Pollution events in PM10 (defined as concentrations > 12 μg m−3) were on average dominated by NH4+ and NO3-, where smaller loadings at the site tended to be dominated by sea salt. As with other western European sites, the charge balance of the inorganic components resolved were biased towards cations, suggesting the aerosol was basic or more likely that organic acids contributed to the charge balance. This study demonstrates the UK background atmospheric composition is primarily driven by meteorology with sea salt dominating air masses from the Atlantic Ocean and the Arctic, whereas secondary inorganic aerosols tended to dominate air masses from continental Europe.

The effect of a post-industrial megacity on local and regional air quality was assessed via a month-long field measurement campaign in the Paris metropolitan area during winter 2010. Here we present source apportionment results from three aerosol mass spectrometers and two aethalometers deployed at three measurement stations within the Paris region. Submicron aerosol composition is dominated by the organic fraction (30–36%) and nitrate (28–29%), with lower contributions from sulfate (14–16%), ammonium (12–14%) and black carbon (7–13%). Organic source apportionment was performed using positive matrix factorization, resulting in a set of organic factors corresponding both to primary emission sources and secondary production. The dominant primary sources are traffic (11–15% of organic mass), biomass burning (13–15%) and cooking (up to 35% during meal hours). Secondary organic aerosol contributes more than 50% to the total organic mass and includes a highly oxidized factor from indeterminate and/or diverse sources and a less oxidized factor related to wood burning emissions. Black carbon was apportioned to traffic and wood burning sources using a model based on wavelength-dependent light absorption of these two combustion sources. The time series of organic and black carbon factors from related sources were strongly correlated. The similarities in aerosol composition, total mass and temporal variation between the three sites suggest that particulate pollution in Paris is dominated by regional factors, and that the emissions from Paris itself have a relatively low impact on its surroundings.

The REgents PARk and Tower Environmental Experiment (REPARTEE) comprised two campaigns in London in October 2006 and October/November 2007. The experiment design involved measurements at a heavily trafficked roadside site, two urban background sites and an elevated site at 160–190 m above ground on the BT Tower, supplemented in the second campaign by Doppler lidar measurements of atmospheric vertical structure. A wide range of measurements of airborne particle physical metrics and chemical composition were made as well as measurements of a considerable range of gas phase species and the fluxes of both particulate and gas phase substances. Significant findings include (a) demonstration of the evaporation of traffic-generated nanoparticles during both horizontal and vertical atmospheric transport; (b) generation of a large base of information on the fluxes of nanoparticles, accumulation mode particles and specific chemical components of the aerosol and a range of gas phase species, as well as the elucidation of key processes and comparison with emissions inventories; (c) quantification of vertical gradients in selected aerosol and trace gas species which has demonstrated the important role of regional transport in influencing concentrations of sulphate, nitrate and secondary organic compounds within the atmosphere of London; (d) generation of new data on the atmospheric structure and turbulence above London, including the estimation of mixed layer depths; (e) provision of new data on trace gas dispersion in the urban atmosphere through the release of purposeful tracers; (f) the determination of spatial differences in aerosol particle size distributions and their interpretation in terms of sources and physico-chemical transformations; (g) studies of the nocturnal oxidation of nitrogen oxides and of the diurnal behaviour of nitrate aerosol in the urban atmosphere, and (h) new information on the chemical composition and source apportionment of particulate matter size fractions in the atmosphere of London derived both from bulk chemical analysis and aerosol mass spectrometry with two instrument types.

Managed grasslands are known to be an important source of N2O with estimated global losses of 2.5 Tg N2O-N yr−1. Chambers are to date the most widely used method to measure N2O fluxes, but also micrometeorological methods are successfully applied. In this paper we present a comparison of N2O fluxes measured by non-steady state chambers and eddy covariance (EC) (using an ultra-sonic anemometer coupled with a tunable diode laser) from an intensively grazed and fertilised grassland site in South East Scotland. The measurements were taken after fertilisation events in 2003, 2007 and 2008. In four out of six comparison periods, a short-lived increase of N2O emissions was observed after mineral N application, returning to background level within 2–6 days. Highest fluxes were measured by both methods in July 2007 with maximum values of 1438 ng N2O-N m−2 s−1 (EC) and 651 ng N2O-N m−2 s−1 (chamber method). Negative fluxes above the detection limit were observed in all comparison periods by EC, while with chambers, the recorded negative fluxes were always below detection limit. Median and average fluxes over each period were always positive. Over all 6 comparison periods, 69% of N2O fluxes measured by EC at the time of chamber closure were within the range of the chamber measurements. N2O fluxes measured by EC during the time of chamber closure were not consistently smaller, neither larger, compared to those measured by chambers: this reflects the fact that the different techniques integrate fluxes over different spatial and temporal scales. Large fluxes measured by chambers may be representing local hotspots providing a small contribution to the flux measured by the EC method which integrates over a larger area. The spatial variability from chamber measurements was high, as shown by a coefficient of variation of up to 139%. No diurnal pattern of N2O fluxes was observed, possibly due to the small diurnal variations of soil temperature. The calculation of cumulative fluxes using different integration methods showed EC data provide generally lower estimates of N2O emissions than chambers.

This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs) from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS), measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 %) of all emitted BVOCs measured, at up to 30 mg m−2 h−1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) exhibited clear deposition of 1 mg m−2 h−1, with a small average canopy resistance of 230 s m−1. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m−2 h−1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m−2 h−1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010), we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.

In April–July 2008, intensive measurements were made of atmospheric composition and chemistry in Sabah, Malaysia, as part of the "Oxidant and particle photochemical processes above a South-East Asian tropical rainforest" (OP3) project. Fluxes and concentrations of trace gases and particles were made from and above the rainforest canopy at the Bukit Atur Global Atmosphere Watch station and at the nearby Sabahmas oil palm plantation, using both ground-based and airborne measurements. Here, the measurement and modelling strategies used, the characteristics of the sites and an overview of data obtained are described. Composition measurements show that the rainforest site was not significantly impacted by anthropogenic pollution, and this is confirmed by satellite retrievals of NO2 and HCHO. The dominant modulators of atmospheric chemistry at the rainforest site were therefore emissions of BVOCs and soil emissions of reactive nitrogen oxides. At the observed BVOC:NOx volume mixing ratio (~100 pptv/pptv), current chemical models suggest that daytime maximum OH concentrations should be ca. 105 radicals cm−3, but observed OH concentrations were an order of magnitude greater than this. We confirm, therefore, previous measurements that suggest that an unexplained source of OH must exist above tropical rainforest and we continue to interrogate the data to find explanations for this.

No abstract available.