The Izaña Atmospheric Research Center (IARC), which is part of the State Meteorological Agency of Spain (AEMET), is a site of excellence in atmospheric science. It manages four observatories in Tenerife including the high altitude Izaña Atmospheric Observatory. The Izaña Atmospheric Observatory was inaugurated in 1916 and since that date has carried out uninterrupted meteorological and climatological observations, contributing towards a unique 100-year record in 2016. This reports are a summary of the many activities at the Izaña Atmospheric Research Center to the broader community. The combination of operational activities, research and development in state-of-the-art measurement techniques, calibration and validation and international cooperation encompass the vision of WMO to provide world leadership in expertise and international cooperation in weather, climate, hydrology and related environmental issues.

An analysis of the 22-yr ozone (O3) series (1988–2009) at the subtropical high mountain Izaña~station (IZO; 2373 m a.s.l.), representative of free troposphere (FT) conditions, is presented. Diurnal and seasonal O3 variations as well as the O3 trend (0.19 ± 0.05 % yr−1 or 0.09 ppbv yr−1), are assessed. A climatology of O3 transport pathways using backward trajectories shows that higher O3 values are associated with air masses travelling above 4 km altitude from North America and North Atlantic Ocean, while low O3 is transported from the Saharan continental boundary layer (CBL). O3 data have been compared with PM10, 210Pb, 7Be, potential vorticity (PV) and carbon monoxide (CO). A clear negative logarithmic relationship was observed between PM10 and surface O3 for all seasons. A similar relationship was found between O3 and 210Pb. The highest daily O3 values (90th percentile) are observed in spring and in the first half of summer time. A positive correlation between O3 and PV, and between O3 and 7Be is found throughout the year, indicating that relatively high surface O3 values at IZO originate from the middle and upper troposphere. We find a good correlation between O3 and CO in winter, supporting the hypothesis of long-range transport of photochemically generated O3 from North America. Aged air masses, in combination with sporadic inputs from the upper troposphere, are observed in spring, summer and autumn. In summer time high O3 values seem to be the result of stratosphere-to-troposphere (STT) exchange processes in regions neighbouring the Canary Islands. Since 1995–1996, the North Atlantic Oscillation has changed from a predominantly high positive phase to alternating between negative, neutral or positive phases. This change results in an increased flow of the westerlies in the mid-latitude and subtropical North Atlantic, thus favouring the transport of O3 and its precursors from North America, and a higher frequency of storms over North Atlantic, with a likely higher incidence of STT processes in mid-latitudes. These processes lead to an increase of tropospheric O3 in the subtropical North Atlantic region after 1996 that has been reflected in surface O3 records at IZO.

Chemically speciated concentrations of PM2.5 (sulphate, ammonium, nitrate, elemental and organic carbon) were simulated in south-west Europe using the three-dimensional air quality model CAMx driven by the MM5 meteorological model. The inner domain covered the south-west region of Spain with a high spatial (2 km x 2 km) and temporal resolution (1 h). The simulation results were evaluated against experimental data obtained in four intensive field campaigns performed in 2008 and 2009 at urban and rural sites. PM2.5 measurements of secondary inorganic compounds and carbonaceous aerosol plus a suite of major and trace elements were determined. High time resolution (10 mm) measurements of Black Carbon (BC) were also conducted. The model captured the variability in the ammonium concentrations in both summer and winter periods, although it tended to underestimate the magnitude of concentrations, while for sulphate the performance was better during the summer periods. Particulate ammonium nitrate was only simulated in significant concentrations in the wintertime campaign. This was found to be consistent with the measured composition of PM2.5 where most of nitrate (79-94%) and a significant fraction of sulphate (24-37%) were estimated to be present as non-ammonium salts. These non-ammonium nitrate salts were attributed to the formation of NaNO3. The model PM2.5 primary elemental carbon simulations, evaluated with hourly resolution, captured the diurnal and seasonal variability of PM2.5 BC concentrations at the urban site while poorer performance was observed at the rural site. A large underestimation was observed for simulated PM2.5 organic carbon concentrations during all campaigns. Scenarios of pollution events linked to emissions from south-west Spain, shipping and contributions from more distant emission sources such as Portugal were identified. These results highlight how the distinct features of PM2.5 composition in southern Europe regions, such as the large contribution of non-ammonium salts, need to be taken into account both in model evaluation and in future implementation of aerosol modelling systems. (C) 2013 Elsevier Ltd. All rights reserved.

Objectives: To demonstrate the importance of thorough investigation of patients with Horner syndrome, and to explain the relevant anatomy.Case report: A 46-year-old man presented with right-sided Horner syndrome. No other abnormality was found. Magnetic resonance imaging showed calcification of the stylohyoid ligament, with a pseudoarthrosis in the mid-portion of the ligament. This pseudoarthrosis was displacing and compressing the internal carotid artery and the adjacent sympathetic chain, causing Horner syndrome.Conclusion: In this case, magnetic resonance imaging was invaluable in elucidating the cause of the Horner syndrome. This is the first described case of pseudoarthrosis of a calcified stylohyoid ligament causing Horner syndrome.

Quantification of ammonia (NH3) land-atmosphere exchange is required for atmospheric modelling and assessment of nitrogen deposition, yet flux measurement methods remain highly uncertain. To address this issue, a major inter-comparison of ammonia fluxes over intensively managed grassland was conducted during the GRAMINAE Integrated Experiment held in Braunschweig, Germany. In order to provide a robust dataset of ammonia exchange with the vegetation, four independent continuous flux gradient systems were operated. Three independently operated continuous wet denuders systems (AMANDA) were compared with a Wet Effluent Diffusion Denuder (mini-WEDD) system. Measurements were made at two distances from an adjacent livestock farm, allowing effects of advection to be quantified in a real landscape setting. Data treatment included filtering for instrument failure, disturbed wind sectors and unsuitable micrometeorological conditions, with corrections made for storage and advection errors.The inter-comparison demonstrated good agreement in measured ammonia concentrations and fluxes (relative standard error <20%) for some periods, although the performance of the ammonia analyzers were variable, with much poorer agreement on particular days. However, by using four systems, the inter-comparison was able to provide a robust mean estimate of continuous ammonia fluxes through the experiment. The observed fluxes were: a) small bi-directional fluxes prior to cutting (−64 to 42 ng NH3 m−2 s−1), b) larger diurnally-varying emissions following cutting (−49 to 703 ng NH3 m−2 s−1) and c) much larger emissions following fertilizer application (0 to 3820 ng NH3 m−2 s−1). The results are a salutary reminder of the uncertainty in unreplicated ammonia flux measurements, while the replication of the present study provides a uniquely robust dataset for the evaluation of ammonia exchange processes. It is clear that consistently reliable determination of ammonia concentrations remains the major measurement challenge.

Estimation of NH3 emissions from a naturally ventilated livestock farm using local-scale atmospheric dispersion modelling A. Hensen, B. Loubet, J. Mosquera, W. C. M. van den Bulk, J. W. Erisman, U. Dämmgen, C. Milford, F. J. Löpmeier, P. Cellier, P. Mikuška, and M. A. Sutton The Energy research Centre of the Netherlands (ECN), Petten, The Netherlands Institut National de la Recherche Agronomique (INRA), Thiverval-Grignon, France Federal Agricultural Research Centre, Braunschweig (FAL), Germany Centre for Ecology and Hydrology (CEH), Edinburgh, UK Institute of Analytical Chemistry, ASCE, v.v.i., Brno, Czech Republic now at: Animal Sciences Group (ASG), Wageningen, The Netherlands Received: 11 September 2008 – Accepted: 14 November 2008 – Published: 14 January 2009 Correspondence to: A. Hensen (hensen@ecn.nl) Published by Copernicus Publications on behalf of the European Geosciences Union.

Stomatal ammonia compensation points (χs) of grass species on a mixed fertilized grassland were determined by measurements of apoplastic [NH4+] and [H>+] in the field. Calculated χs values were compared with in-canopy atmospheric NH3 concentration (χa) measurements.Leaf apoplastic [NH4+] increased by a factor of two from the lowest level in the canopy to the top level. Bulk leaf [NH4+] and especially [NO3−] slightly increased at the bottom of the canopy and these concentrations were very high in senescent plant litter. Calculated χs values were below atmospheric χs at all canopy levels measured, indicating that the grassland was characterized by NH3 deposition before cutting. This was confirmed by the χa profile, showing the lowest χa close to the ground (15 cm above soil surface) and an increase in χa with canopy height. Neither χs nor χa could be measured close to the soil surface, however, the [NH4+] in the litter material indicated a high potential for NH3 emission.A diurnal course in apoplastic [NH4+] was seen in the regrowing grass growing after cutting, with highest concentration around noon. Both apoplastic and tissue [NH4+] increased in young grass compared to tall grass. Following cutting, in-canopy gradients of atmospheric χa showed NH3 emission but since calculated χs values of the cut grass were still lower than atmospheric NH3 concentrations, the emissions could not entirely be explained by stomatal NH3 loss. High tissue [NH4+] in the senescent plant material indicated that this fraction constituted an NH3 source. After fertilization, [NH4+] increased both in apoplast and leaf tissue with the most pronounced increase in the former compared to the latter. The diurnal pattern in apoplastic [NH4+] was even more pronounced after fertilization and calculated χs values were generally higher, but remained below atmospheric [NH3].

Abstract. Improved data on biosphere-atmosphere exchange are fundamental to understanding the production and fate of ammonia (NH3) in the atmosphere. The GRAMINAE Integrated Experiment combined novel measurement and modelling approaches to provide the most comprehensive analysis of the interactions to date. Major inter-comparisons of micrometeorological parameters and NH3 flux measurements using the aerodynamic gradient method and relaxed eddy accumulation (REA) were conducted. These showed close agreement, though the REA systems proved insufficiently precise to investigate vertical flux divergence. Grassland management had a large effect on fluxes: emissions increased after grass cutting (−50 to 700 ng m−2 s−1 NH3) and after N-fertilization (0 to 3800 ng m−2 s−1) compared with before the cut (−60 to 40 ng m−2 s−1). Effects of advection and air chemistry were investigated using horizontal NH3 profiles, acid gas and particle flux measurements. Inverse modelling of NH3 emission from an experimental farm agreed closely with inventory estimates, while advection errors were used to correct measured grassland fluxes. Advection effects were caused both by the farm and by emissions from the field, with an inverse dispersion-deposition model providing a reliable new approach to estimate net NH3 fluxes. Effects of aerosol chemistry on net NH3 fluxes were small, while the measurements allowed NH3-induced particle growth rates to be calculated and aerosol fluxes to be corrected. Bioassays estimated the emission potential Γ = [NH4+]/[H+] for different plant pools, with the apoplast having the smallest values (30–1000). The main within-canopy sources of NH3 emission appeared to be leaf litter and the soil surface, with Γ up to 3 million and 300 000, respectively. Cuvette and within-canopy analyses confirmed the role of leaf litter NH3 emission, which, prior to cutting, was mostly recaptured within the canopy. Measured ammonia fluxes were compared with three models: an ecosystem model (PaSim), a soil vegetation atmosphere transfer model (SURFATM-NH3) and a dynamic leaf chemistry model (DCC model). The different models each reproduced the main temporal dynamics in the flux, highlighting the importance of canopy temperature dynamics (Surfatm-NH3), interactions with ecosystem nitrogen cycling (PaSim) and the role of leaf surface chemistry (DCC model). Overall, net above-canopy fluxes were mostly determined by stomatal and cuticular uptake (before the cut), leaf litter emissions (after the cut) and fertilizer and litter emissions (after fertilization). The dynamics of ammonia emission from leaf litter are identified as a priority for future research.

A major international experiment on ammonia (NH3) biosphere-atmosphere exchange was conducted over intensively managed grassland at Braunschweig, Germany. The experimental strategy was developed to allow an integrated analysis of different features of NH3 exchange including: a) quantification of nearby emissions and advection effects, b) estimation of net NH3 fluxes with the canopy by a range of micrometeorological measurements, c) analysis of the sources and sinks of NH3 within the plant canopy, including soils and bioassay measurements, d) comparison of the effects of grassland management options on NH3 fluxes and e) assessment of the interactions of NH3 fluxes with aerosol exchange processes. Additional technical objectives included the inter-comparison of different estimates of sensible and latent heat fluxes, as well as continuous-gradient and Relaxed Eddy Accumulation (REA) systems for NH3 fluxes.The prior analysis established the spatial and temporal design of the experiment, allowing significant synergy between these objectives. The measurements were made at 7 measurement locations, thereby quantifying horizontal and vertical profiles, and covered three phases: a) tall grass canopy prior to cutting (7 days), b) short grass after cutting (7 days) and c) re-growing sward following fertilization with ammonium nitrate (10 days). The sequential management treatments allowed comparison of sources-sinks, advection and aerosol interactions under a wide range of NH3 fluxes.This paper describes the experimental strategy and reports the grassland management history, soils, environmental conditions and air chemistry during the experiment, finally summarizing how the results are coordinated in the accompanying series of papers.

Agricultural livestock represents the main source of ammonia (NH3) in Europe. In recent years, reduction policies have been applied to reduce NH3 emissions. In order to estimate the impacts of these policies, robust estimates of the emissions from the main sources, i.e. livestock farms are needed. In this paper, the NH3 emissions were estimated from a naturally ventilated livestock farm in Braunschweig, Germany during a joint field experiment of the GRAMINAE European project. An inference method was used with a Gaussian-3D plume model and with the Huang 3-D model. NH3 concentrations downwind of the source were used together with micrometeorological data to estimate the source strength over time. Mobile NH3 concentration measurements provided information on the spatial distribution of source strength. The estimated emission strength ranged between 6.4±0.18 kg NH3 d−1 (Huang 3-D model) and 9.2±0.7 kg NH3 d−1 (Gaussian-3D model). These estimates were 94% and 63% of what was obtained using emission factors from the German national inventory (9.6 kg d−1 NH3). The effect of deposition was evaluated with the FIDES-2D model. This increased the emission estimate to 11.7 kg NH3 d−1, showing that deposition can explain the observed difference. The daily pattern of the source was correlated with net radiation and with the temperature inside the animal houses. The daily pattern resulted from a combination of a temperature effect on the source concentration together with an effect of variations in free and forced convection of the building ventilation rate. Further development of the plume technique is especially relevant for naturally ventilated farms, since the variable ventilation rate makes other emission measurements difficult.

Abstract. Deposition of atmospheric ammonia (NH3) to semi-natural ecosystems leads to serious adverse effects, such as acidification and eutrophication. A step in quantifying such effects is the measurement of NH3 fluxes over semi-natural and agricultural land. However, measurement of NH3 fluxes over vegetation in the vicinity of strong NH3 sources is challenging, since NH3 emissions are highly heterogeneous. Indeed, under such conditions, local advection errors may alter the measured fluxes. In this study, local advection errors (ΔFz,adv) were estimated over a 14 ha grassland field, which was successively cut and fertilised, as part of the GRAMINAE integrated Braunschweig experiment. The magnitude of ΔFz,adv was determined up to 810 m downwind from farm buildings emitting between 6.2 and 9.9 kg NH3 day−1. The GRAMINAE experiment provided a unique opportunity to compare two methods of estimating ΔFz,adv: one inference method based on measurements of horizontal concentration gradients, and one based on inverse dispersion modelling with a two-dimensional model. Two sources of local advection were clearly identified: the farm NH3 emissions leading to positive ΔFz,adv ("bias towards emissions") and field NH3 emissions, which led to a negative ΔFz,adv ("bias towards deposition"). The local advection flux from the farm was in the range 0 to 27 ng NH3 m−2 s−1 at 610 m from the farm, whereas ΔFz,adv due to field emission was proportional to the local flux, and ranged between −209 and 13 ng NH3 m−2 s−1. The local advection flux ΔFz,adv was either positive or negative depending on the magnitude of these two contributions. The modelled and inferred advection errors agreed well. The inferred advection errors, relative to the vertical flux at 1 m height, were 52% on average, before the field was cut, and less than 2.1% when the field was fertilised. The variability of the advection errors in response to changes in micrometeorological conditions is also studied. The limits of the 2-D modelling approach are discussed.

In the frame of the WMO Global Atmosphere Watch Urban Research Meteorology and Environment programme (GURME), a system for forecasting air pollution episode potential in the Canary Islands has been developed. Meteorological parameters relevant to air quality (synoptic wind speed, wind direction, boundary layer height and temperature at 91 vertical levels) are obtained from the European Centre for Medium range Weather Forecasting (ECMWF) once a day for up to four days ahead. In addition, a model based on the analogue method utilising six years of historical meteorological and air quality data predicts the probability of SO2 concentration exceeding certain thresholds for a measurement station located in Santa Cruz de Tenerife. Meteorological forecasts are also provided from a high resolution (2 km) local area model (MM5) implemented for the Canary Islands domain. This simple system is able to forecast meteorological conditions which are favourable to the occurrence of pollution episodes for the forthcoming days.

Ammonia emissions from two contrasting seabird colonies in Scotland were measured, based on the determination of atmospheric concentrations downwind of the colonies. Atmospheric concentrations of ammonia (NH3) across the downwind plume were compared with the inverse application of a Gaussian dispersion model (ID) to calculate the modelled NH3 emission that would generate the measured cross-wind-integrated plume concentration. In parallel, a tracer gas (sulphur hexafluoride, SF6) was released from the colonies with air samples taken to allow determination of SF6 concentrations. On the basis of the known emission rate of SF6, the magnitude of ammonia emissions was estimated by the cross-wind-integrated tracer ratio (TR) of NH3/SF6 concentrations. Coupled with data on annual bird attendance, the measurements indicate annual emissions from the Isle of May and the Bass Rock of 18 and 132 tonnes NH3-N year-1, respectively. The measured NH3 emissions were compared with estimates of seabird nitrogen excretion to estimate the proportion of excreted N that is volatilised as NH3 (FNr). The emission estimates of the two methods compared favourably, giving 4 and 6 kg NH3-N h-1 (FNr = 15%) for the Isle of May for the ID and TR methods, respectively, and 21 and 25 kg NH3-N h-1 (FNr = 50%) for the Bass Rock for the ID and TR methods, respectively. The results provide the first measurement-based estimates to allow regional up scaling of ammonia emissions from seabirds.

Field measurements of NH3 fluxes using an eddy covariance technique were made for a total of 60 days between July and September 2002 at an intensively managed grassland in Southern Scotland. The collected data demonstrate the suitability of a tuneable diode laser absorption spectroscopy (TDLAS) system coupled with a sonic anemometer for eddy covariance measurements. The novelty of these measurements is the application to ammonia, which has only become measurable using TDLAS techniques recently, because of its small ambient concentration. Data presented in this paper show typical features of the fluxes and concentration for the summer season. NH3 concentration and flux values are in a similar range to previous studies using flux gradient methods at the same field site, although the particularly wet season reduced the concentration of NH3 in the air. For an example day, measured NH3 fluxes ranged between –11 and 44 ng m–2 s–1 with an average value of 3.78 ng m–2 s–1 indicating a small net emission from the vegetation. Spectral analysis executed on the data shows the percentage of flux carried by the small eddies (from 0.2 to 2 m) suggesting that high detection frequency instruments are particularly suitable for estimating NH3 fluxes between atmosphere and vegetation.

A new study to address the biosphere-atmosphere exchange of ammonia (NH3) with grasslands is applying a European transect to interpret NH3 fluxes in relation to atmospheric conditions, grassland management and soil chemistry. Micrometeorological measurements using the aerodynamic gradient method (AGM) with continuous NH3 detectors are supported by bioassays of the NH3 `stomatal compensation point' (χs). Relaxed eddy accumulation (REA) is also applied to enable flux measurements at one height; this is relevant to help address flux divergence due to gas-particle inter-conversion or the presence of local sources in a landscape.