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A comprehensive European dataset on monthly atmospheric NH3, acid gases (HNO3, SO2, HCl), and aerosols (NH4+, NO3-, SO42-, Cl−, Na+, Ca2+, Mg2+) is presented and analysed. Speciated measurements were made with a low-volume denuder and filter pack method (DEnuder for Long-Term Atmospheric sampling, DELTA®) as part of the EU NitroEurope (NEU) integrated project. Altogether, there were 64 sites in 20 countries (2006–2010), coordinated between seven European laboratories. Bulk wet-deposition measurements were carried out at 16 co-located sites (2008–2010). Inter-comparisons of chemical analysis and DELTA® measurements allowed an assessment of comparability between laboratories. The form and concentrations of the different gas and aerosol components measured varied between individual sites and grouped sites according to country, European regions, and four main ecosystem types (crops, grassland, forests, and semi-natural). The smallest concentrations (with the exception of SO42- and Na+) were in northern Europe (Scandinavia), with broad elevations of all components across other regions. SO2 concentrations were highest in central and eastern Europe, with larger SO2 emissions, but particulate SO42- concentrations were more homogeneous between regions. Gas-phase NH3 was the most abundant single measured component at the majority of sites, with the largest variability in concentrations across the network. The largest concentrations of NH3, NH4+, and NO3- were at cropland sites in intensively managed agricultural areas (e.g. Borgo Cioffi in Italy), and the smallest were at remote semi-natural and forest sites (e.g. Lompolojänkkä, Finland), highlighting the potential for NH3 to drive the formation of both NH4+ and NO3- aerosol. In the aerosol phase, NH4+ was highly correlated with both NO3- and SO42-, with a near-1:1 relationship between the equivalent concentrations of NH4+ and sum (NO3-+ SO42-), of which around 60 % was as NH4NO3. Distinct seasonality was also observed in the data, influenced by changes in emissions, chemical interactions, and the influence of meteorology on partitioning between the main inorganic gases and aerosol species. Springtime maxima in NH3 were attributed to the main period of manure spreading, while the peak in summer and trough in winter were linked to the influence of temperature and rainfall on emissions, deposition, and gas–aerosol-phase equilibrium. Seasonality in SO2 was mainly driven by emissions (combustion), with concentrations peaking in winter, except in southern Europe, where the peak occurred in summer. Particulate SO42- showed large peaks in concentrations in summer in southern and eastern Europe, contrasting with much smaller peaks occurring in early spring in other regions. The peaks in particulate SO42- coincided with peaks in NH3 concentrations, attributed to the formation of the stable (NH4)2SO4. HNO3 concentrations were more complex, related to traffic and industrial emissions, photochemistry, and HNO3:NH4NO3 partitioning. While HNO3 concentrations were seen to peak in the summer in eastern and southern Europe (increased photochemistry), the absence of a spring peak in HNO3 in all regions may be explained by the depletion of HNO3 through reaction with surplus NH3 to form the semi-volatile aerosol NH4NO3. Cooler, wetter conditions in early spring favour the formation and persistence of NH4NO3 in the aerosol phase, consistent with the higher springtime concentrations of NH4+ and NO3-. The seasonal profile of NO3- was mirrored by NH4+, illustrating the influence of gas–aerosol partitioning of NH4NO3 in the seasonality of these components. Gas-phase NH3 and aerosol NH4NO3 were the dominant species in the total inorganic gas and aerosol species measured in the NEU network. With the current and projected trends in SO2, NOx, and NH3 emissions, concentrations of NH3 and NH4NO3 can be expected to continue to dominate the inorganic pollution load over the next decades, especially NH3, which is linked to substantial exceedances of ecological thresholds across Europe. The shift from (NH4)2SO4 to an atmosphere more abundant in NH4NO3 is expected to maintain a larger fraction of reactive N in the gas phase by partitioning to NH3 and HNO3 in warm weather, while NH4NO3 continues to contribute to exceedances of air quality limits for PM2.5.

The Auchencorth Moss atmospheric observatory has being measuring meteorological parameters since 1995. The site was originally set‐up to measure the deposition of sulphur dioxide at a site that represented the vegetation and climate typical of NW Europe, in relatively clean background air. It is one of the longest running flux monitoring sites in the region, over semi‐natural vegetation, providing infrastructure and support for many measurement campaigns and continuous monitoring of air pollutants and greenhouse gases. The meteorological sensors that are used, data processing and quality reviewing procedures are described for a set of core measurements up to 2016. These core measurements are essential for the interpretation of the other atmospheric variables. Open Practices This article has earned an Open Data badge for making publicly available the digitally‐shareable data necessary to reproduce the reported results. The data is available at http://catalogue.ceda.ac.uk/uuid/8e6cbb111cfd41a19c92aadcb2d040fd. Learn more about the Open Practices badges from the Center for Open Science: https://osf.io/tvyxz/wiki.

The fast economic development of southwest China has resulted in significant increases in the concentrations of reactive nitrogen (Nr) in the atmosphere. In this study, an urban (Chengdu, CD), suburban (Shifang, SF) and agriculture (Yanting, YT) – dominated location in the Sichuan Province, southwest China, were selected to investigate the atmospheric composition of Nr, their concentrations and deposition rates. We measured Nr concentrations in precipitation (NH4+, NO3− and organic N (DON)), the gas phase (NH3 and NO2), and the aerosol particles (PM2.5), and calculated their fluxes over a two year period (2014–2016). Total annual N deposition rates were 49.2, 44.7 and 19.8 kg N ha−1 yr−1 at CD, SF and YT, respectively. Ammonia concentrations were larger at the urban and suburban sites than the agricultural site (12.2, 14.9, and 4.9 μg N m−3 at CD, SF and YT, respectively). This is consistent with the multitude of larger sources of NH3, including city garbage, livestock and traffic, in the urban and suburban areas. Monthly NO2 concentrations were lower in warmer compared to the colder months, but seasonal differences were insignificant. Daily PM2.5 concentrations ranged from 7.7 to 236.0, 5.0–210.4 and 4.2–128.4 μg m−3 at CD, SF and YT, respectively, and showed significant correlations with fine particulate NH4+ and NO3− concentrations. Ratios of reduced to oxidized N were in the range of 1.6–2.7. This implies that the control of reduced Nr especially in urban environments is needed to improve local air quality.

In this study the GAG model, a process-based ammonia (NH3) emission model for urine patches, was extended and applied for the field scale. The new model (GAG_field) was tested over two modelling periods, for which micrometeorological NH3 flux data were available. Acknowledging uncertainties in the measurements, the model was able to simulate the main features of the observed fluxes. The temporal evolution of the simulated NH3 exchange flux was found to be dominated by NH3 emission from the urine patches, offset by simultaneous NH3 deposition to areas of the field not affected by urine. The simulations show how NH3 fluxes over a grazed field in a given day can be affected by urine patches deposited several days earlier, linked to the interaction of volatilization processes with soil pH dynamics. Sensitivity analysis showed that GAG_field was more sensitive to soil buffering capacity (β), field capacity (θfc) and permanent wilting point (θpwp) than the patch-scale model. The reason for these different sensitivities is dual. Firstly, the difference originates from the different scales. Secondly, the difference can be explained by the different initial soil pH and physical properties, which determine the maximum volume of urine that can be stored in the NH3 source layer. It was found that in the case of urine patches with a higher initial soil pH and higher initial soil water content, the sensitivity of NH3 exchange to β was stronger. Also, in the case of a higher initial soil water content, NH3 exchange was more sensitive to the changes in θfc and θpwp. The sensitivity analysis showed that the nitrogen content of urine (cN) is associated with high uncertainty in the simulated fluxes. However, model experiments based on cN values randomized from an estimated statistical distribution indicated that this uncertainty is considerably smaller in practice. Finally, GAG_field was tested with a constant soil pH of 7.5. The variation of NH3 fluxes simulated in this way showed a good agreement with those from the simulations with the original approach, accounting for a dynamically changing soil pH. These results suggest a way for model simplification when GAG_field is applied later at regional scale.

Laboratory experiments suggest that water-soluble products from the gas-phase oxidation of volatile organic compounds can partition into atmospheric waters where they are further oxidized to form low volatility products, providing an alternative route for oxidation in addition to further oxidation in the gas phase. These products can remain in the particle phase after water evaporation, forming what is termed as aqueous secondary organic aerosol (aqSOA). However, few studies have attempted to observe ambient aqSOA. Therefore, a suite of measurements, including near-real-time WSOC (water-soluble organic carbon), inorganic anions/cations, organic acids, and gas-phase glyoxal, were made during the PEGASOS (Pan-European Gas-AeroSOls-climate interaction Study) 2012 campaign in the Po Valley, Italy, to search for evidence of aqSOA. Our analysis focused on four periods: Period A on 19–21 June, Period B on 30 June and 1–2 July, Period C on 3–5 July, and Period D on 6–7 July to represent the first (Period A) and second (Periods B, C, and D) halves of the study. These periods were picked to cover varying levels of WSOC and aerosol liquid water. In addition, back trajectory analysis suggested all sites sampled similar air masses on a given day. The data collected during both periods were divided into times of increasing relative humidity (RH) and decreasing RH, with the aim of diminishing the influence of dilution and mixing on SOA concentrations and other measured variables. Evidence for local aqSOA formation was only observed during Period A. When this occurred, there was a correlation of WSOC with organic aerosol (R2 = 0.84), aerosol liquid water (R2 = 0.65), RH (R2 = 0.39), and aerosol nitrate (R2 = 0.66). Additionally, this was only observed during times of increasing RH, which coincided with dark conditions. Comparisons of WSOC with oxygenated organic aerosol (OOA) factors, determined from application of positive matrix factorization analysis on the aerosol mass spectrometer observations of the submicron non-refractory organic particle composition, suggested that the WSOC differed in the two halves of the study (Period A WSOC vs. OOA-2 R2 = 0.83 and OOA-4 R2 = 0.04, whereas Period C WSOC vs. OOA-2 R2 = 0.03 and OOA-4 R2 = 0.64). OOA-2 had a high O ∕ C (oxygen ∕ carbon) ratio of 0.77, providing evidence that aqueous processing was occurring during Period A. Key factors of local aqSOA production during Period A appear to include air mass stagnation, which allows aqSOA precursors to accumulate in the region; the formation of substantial local particulate nitrate during the overnight hours, which enhances water uptake by the aerosol; and the presence of significant amounts of ammonia, which may contribute to ammonium nitrate formation and subsequent water uptake and/or play a more direct role in the aqSOA chemistry.

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, HNO 3 , SO 2 and NH 3 , and their associated water-soluble aerosol counterparts Cl − , NO 2 − , NO 3 − , SO 4 2− , NH 4 + as determined hourly for one month in May–June 2016 over agricultural grassland pre- and post-fertilisation. Measurements were made using the Gradient of Aerosols and Gases Online Registration (GRAEGOR) wet–chemical two–point gradient instrument. Emissions of NH 3 peaked at 1460 ng m −2 s −1 three hours after fertilisation, with an emission of HONO peaking at 4.92 ng m −2 s −1 occurring five hours after fertilisation. Apparent emissions of NO 3 − aerosol were observed after fertilisation which, coupled with a divergence of HNO 3 deposition velocity ( V d ) from its theoretical maximum value, suggested the reaction of emitted NH 3 with atmospheric HNO 3 to form ammonium nitrate aerosol. The use of the conservative exchange fluxes of tot-NH 4 + and tot-NO 3 − indicated net emission of tot-NO 3 − , implying a ground source of HNO 3 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 V d of NH 4 + was with 0.93 mm/s in the range expected for the accumulation mode, the larger average V d for Cl − (3.65 mm/s), NO 3 − (1.97 mm/s), SO 4 2− (1.89 mm/s) reflected the contribution of a super-micron fraction and decreased with increasing PM 2.5 / PM 10 ratio (a proxy measurement for aerosol size), providing direct evidence of a size-dependence of aerosol deposition velocity for aerosol chemical compounds.

The environmental impacts of ammonia (NH3) in ambient air have become more evident in the recent decades, leading to intensifying research in this field. A number of novel analytical techniques and monitoring instruments have been developed, and the quality and availability of reference gas mixtures used for the calibration of measuring instruments has also increased significantly. However, recent inter-comparison measurements show significant discrepancies, indicating that the majority of the newly developed devices and reference materials require further thorough validation. There is a clear need for more intensive metrological research focusing on quality assurance, intercomparability and validations. MetNH3 (Metrology for ammonia in ambient air) is a three-year project within the framework of the European Metrology Research Programme (EMRP), which aims to bring metrological traceability to ambient ammonia measurements in the 0.5-500 nmol mol-1 amount fraction range. This is addressed by working in three areas: (1) improving accuracy and stability of static and dynamic reference gas mixtures, (2) developing an optical transfer standard and (3) establishing the link between high-accuracy metrological standards and field measurements. In this article we describe the concept, aims and first results of the project.

Volcanic emissions, specifically from Iceland, pose a pan-European risk and are on the UK National Risk Register due to potential impacts on aviation, public health, agriculture, the environment and the economy, from both effusive and explosive activity. During the 2014–2015 fissure eruption at Holuhraun in Iceland, the UK atmosphere was significantly perturbed. This study focuses one major incursion in September 2014, affecting the surface concentrations of both aerosols and gases across the UK, with sites in Scotland experiencing the highest sulfur dioxide (SO2) concentrations. The perturbation event observed was confirmed to originate from the fissure eruption using satellite data from GOME2B and the chemical transport model, EMEP4UK, which was used to establish the spatial distribution of the plume over the UK during the event of interest. At the two UK European Monitoring and Evaluation Program (EMEP) supersite observatories (Auchencorth Moss, SE Scotland, and Harwell, SE England) significant alterations in sulfate (SO42−) content of PM10 and PM2.5 during this event, concurrently with evidence of an increase in ultrafine aerosol most likely due to nucleation and growth of aerosol within the plume, were observed. At Auchencorth Moss, higher hydrochloric acid (HCl) concentrations during the September event (max = 1.21 µg m−3, cf. annual average 0.12 µg m−3 in 2013), were assessed to be due to acid displacement of chloride (Cl−) from sea salt (NaCl) to form HCl gas rather than due to primary emissions of HCl from Holuhraun. The gas and aerosol partitioning at Auchencorth Moss of inorganic species by thermodynamic modelling confirmed the observed partitioning of HCl. Using the data from the chemical thermodynamic model, ISORROPIA-II, there is evidence that the background aerosol, which is typically basic at this site, became acidic with an estimated pH of 3.8 during the peak of the event.Volcano plume episodes were periodically observed by the majority of the UK air quality monitoring networks during the first 4 months of the eruption (August–December 2014), at both hourly and monthly resolution. In the low-resolution networks, which provide monthly SO2 averages, concentrations were found to be significantly elevated at remote “clean” sites in NE Scotland and SW England, with record-high SO2 concentrations for some sites in September 2014. For sites which are regularly influenced by anthropogenic emissions, taking into account the underlying trends, the eruption led to statistically unremarkable SO2 concentrations (return probabilities > 0.1, ∼ 10 months). However, for a few sites, SO2 concentrations were clearly much higher than has been previously observed (return probability 3000 months). The Holuhraun Icelandic eruption has resulted in a unique study providing direct evidence of atmospheric chemistry perturbation of both gases and aerosols in the UK background atmosphere. The measurements can be used to both challenge and verify existing atmospheric chemistry of volcano plumes, especially those originating from effusive eruptions, which have been underexplored due to limited observations available in the literature. If all European data sets were collated this would allow improved model verification and risk assessments for future volcanic eruptions of this type.

This work presents 15-min averaged measurements of peroxyacetyl nitrate (PAN) obtained during spring 2014 (24/04/2014 – 06/05/2014) at the Auchencorth UK EMEP supersite (southeast Scotland). The aim of this analysis was to investigate the conditions producing the distribution of PAN mixing ratios at the supersite in spring 2014. Air mass back trajectories showed the majority of air masses to have spent substantial time over the UK, continental Europe or Scandinavia prior to arrival at Auchencorth. The median and 95th percentile PAN mixing ratios observed were 0.46 ppb and 1.03 ppb, respectively. The median mixing ratio was elevated compared with previous PAN measurements during springtime (April–May) in southeast Scotland (corresponding median mixing ratios April–May 1994–1998: 0.1–0.3 ppb), which is hypothesised to be due to conditions conducive to regional (European) photochemical PAN production. Additionally, PAN mixing ratios during regionally influenced conditions (0.4–1.5 ppb) were substantially more elevated from hemispheric background mixing ratios (0.4–0.6 ppb) than for ozone (O3, regional: 10–45 ppb, hemispheric: 30–40 ppb). PAN and O3 both impact upon vegetation and human health and it is necessary to understand the extent to which hemispheric and regional processes contribute to their abundances in different locations. Regional processes can both increase and decrease PAN and O3 mixing ratios compared to imported hemispheric background mixing ratios. This study concludes that during the measurement period in spring 2014 at the Auchencorth supersite, regional PAN and O3 modifying processes enhanced PAN mixing ratios more than for O3.

The global nitrogen (N) cycle at the beginning of the 21st century has been shown to be strongly influenced by the inputs of reactive nitrogen (Nr) from human activities, including combustion-related NOx, industrial and agricultural N fixation, estimated to be 220 Tg N yr−1 in 2010, which is approximately equal to the sum of biological N fixation in unmanaged terrestrial and marine ecosystems. According to current projections, changes in climate and land use during the 21st century will increase both biological and anthropogenic fixation, bringing the total to approximately 600 Tg N yr−1 by around 2100. The fraction contributed directly by human activities is unlikely to increase substantially if increases in nitrogen use efficiency in agriculture are achieved and control measures on combustion-related emissions implemented. Some N-cycling processes emerge as particularly sensitive to climate change. One of the largest responses to climate in the processing of Nr is the emission to the atmosphere of NH3, which is estimated to increase from 65 Tg N yr−1 in 2008 to 93 Tg N yr−1 in 2100 assuming a change in global surface temperature of 5 °C in the absence of increased anthropogenic activity. With changes in emissions in response to increased demand for animal products the combined effect would be to increase NH3 emissions to 135 Tg N yr−1. Another major change is the effect of climate changes on aerosol composition and specifically the increased sublimation of NH4NO3 close to the ground to form HNO3 and NH3 in a warmer climate, which deposit more rapidly to terrestrial surfaces than aerosols. Inorganic aerosols over the polluted regions especially in Europe and North America were dominated by (NH4)2SO4 in the 1970s to 1980s, and large reductions in emissions of SO2 have removed most of the SO42− from the atmosphere in these regions. Inorganic aerosols from anthropogenic emissions are now dominated by NH4NO3, a volatile aerosol which contributes substantially to PM10 and human health effects globally as well as eutrophication and climate effects. The volatility of NH4NO3 and rapid dry deposition of the vapour phase dissociation products, HNO3 and NH3, is estimated to be reducing the transport distances, deposition footprints and inter-country exchange of Nr in these regions. There have been important policy initiatives on components of the global N cycle. These have been regional or country-based and have delivered substantial reductions of inputs of Nr to sensitive soils, waters and the atmosphere. To date there have been no attempts to develop a global strategy to regulate human inputs to the nitrogen cycle. However, considering the magnitude of global Nr use, potential future increases, and the very large leakage of Nr in many forms to soils, waters and the atmosphere, international action is required. Current legislation will not deliver the scale of reductions globally for recovery from the effects of Nr deposition on sensitive ecosystems, or a decline in N2O emissions to the global atmosphere. Such changes would require substantial improvements in nitrogen use efficiency across the global economy combined with optimization of transport and food consumption patterns. This would allow reductions in Nr use, inputs to the atmosphere and deposition to sensitive ecosystems. Such changes would offer substantial economic and environmental co-benefits which could help motivate the necessary actions.

A period of elevated surface concentrations of airborne particulate matter (PM) in the UK in spring 2014 was widely associated in the UK media with a Saharan dust plume. This might have led to over-emphasis on a natural phenomenon and consequently to a missed opportunity to inform the public and provide robust evidence for policy-makers about the observed characteristics and causes of this pollution event. In this work, the EMEP4UK regional atmospheric chemistry transport model (ACTM) was used in conjunction with speciated PM measurements to investigate the sources and long-range transport (including vertical) processes contributing to the chemical components of the elevated surface PM. It is shown that the elevated PM during this period was mainly driven by ammonium nitrate, much of which was derived from emissions outside the UK. In the early part of the episode, Saharan dust remained aloft above the UK; we show that a significant contribution of Saharan dust at surface level was restricted only to the latter part of the elevated PM period and to a relatively small geographic area in the southern part of the UK. The analyses presented in this paper illustrate the capability of advanced ACTMs, corroborated with chemically-speciated measurements, to identify the underlying causes of complex PM air pollution episodes. Specifically, the analyses highlight the substantial contribution of secondary inorganic ammonium nitrate PM, with agricultural ammonia emissions in continental Europe presenting a major driver. The findings suggest that more emphasis on reducing emissions in Europe would have marked benefits in reducing episodic PM2.5 concentrations in the UK.

The NitroEurope project aims to improve understanding of the nitrogen (N) cycle at the continental scale and quantify the major fluxes of reactive N by a combination of reactive N measurements and modelling activities. As part of the overall measurement strategy, a network of 13 flux ‘super sites’ (Level-3) has been established, covering European forest, arable, grassland and wetland sites, with the objective of quantifying the N budget at a high spatial resolution and temporal frequency for 4.5 years, and to estimate greenhouse gas budgets (N2O, CH4 and CO2). These sites are supported by a network of low-cost flux measurements (Level-2, 9 sites) and a network to infer reactive N fluxes at 58 sites (Level-1), for comparison with carbon (C) flux measurements. Measurements at the Level-3 sites include high resolution N2O, NO (also CH4, CO2) fluxes, wet and dry N deposition, leaching of N and C and N transformations in plant, litter and soil. Results for the first 11 months (1.8.2006 to 30.6.2007) suggest that the grasslands are the largest source of N2O, that forests are the largest source of NO and sink of CH4 and that N deposition rates influence NO and N2O fluxes in non-agricultural ecosystems. The NO and N2O emission ratio is influenced by soil type and precipitation. First budgets of reactive N entering and leaving the ecosystem and of net greenhouse gas exchange are outlined. Further information on rates of denitrification to N2 and biological N2 fixation is required to complete the N budgets for some sites. The quantitative roles played by CO2, N2O and CH4 in defining net greenhouse gas exchange differ widely between ecosystems depending on the interactions of climate, soil type, land use and management.

Recent research in nitrogen exchange with the atmosphere has separated research communities according to N form. The integrated perspective needed to quantify the net effect of N on greenhouse-gas balance is being addressed by the NitroEurope Integrated Project (NEU). Recent advances have depended on improved methodologies, while ongoing challenges include gas-aerosol interactions, organic nitrogen and N2 fluxes. The NEU strategy applies a 3-tier Flux Network together with a Manipulation Network of global-change experiments, linked by common protocols to facilitate model application. Substantial progress has been made in modelling N fluxes, especially for N2O, NO and bi-directional NH3 exchange. Landscape analysis represents an emerging challenge to address the spatial interactions between farms, fields, ecosystems, catchments and air dispersion/deposition. European up-scaling of N fluxes is highly uncertain and a key priority is for better data on agricultural practices. Finally, attention is needed to develop N flux verification procedures to assess compliance with international protocols., JRC.H.2-Climate change