In many large cities of Europe standard air quality limit values of particulate matter (PM) are exceeded. Emissions from road traffic and biomass burning are frequently reported to be the major causes. As a consequence of these exceedances a large number of air quality plans, most of them focusing on traffic emissions reductions, have been implemented in the last decade. In spite of this implementation, a number of cities did not record a decrease of PM levels. Thus, is the efficiency of air quality plans overestimated? Do the road traffic emissions contribute less than expected to ambient air PM levels in urban areas? Or do we need a more specific metric to evaluate the impact of the above emissions on the levels of urban aerosols? This study shows the results of the interpretation of the 2009 variability of levels of PM, Black Carbon (BC), aerosol number concentration (N) and a number of gaseous pollutants in seven selected urban areas covering road traffic, urban background, urban-industrial, and urban-shipping environments from southern, central and northern Europe. The results showed that variations of PM and N levels do not always reflect the variation of the impact of road traffic emissions on urban aerosols. However, BC levels vary proportionally with those of traffic related gaseous pollutants, such as CO, NO2 and NO. Due to this high correlation, one may suppose that monitoring the levels of these gaseous pollutants would be enough to extrapolate exposure to traffic-derived BC levels. However, the BC/CO, BC/NO2 and BC/NO ratios vary widely among the cities studied, as a function of distance to traffic emissions, vehicle fleet composition and the influence of other emission sources such as biomass burning. Thus, levels of BC should be measured at air quality monitoring sites. During morning traffic rush hours, a narrow variation in the N/BC ratio was evidenced, but a wide variation of this ratio was determined for the noon period. Although in central and northern Europe N and BC levels tend to vary simultaneously, not only during the traffic rush hours but also during the whole day, in urban background stations in southern Europe maximum N levels coinciding with minimum BC levels are recorded at midday in all seasons. These N maxima recorded in southern European urban background environments are attributed to midday nucleation episodes occurring when gaseous pollutants are diluted and maximum insolation and O3 levels occur. The occurrence of SO2 peaks may also contribute to the occurrence of midday nucleation bursts in specific industrial or shipping-influenced areas, although at several central European sites similar levels of SO2 are recorded without yielding nucleation episodes. Accordingly, it is clearly evidenced that N variability in different European urban environments is not equally influenced by the same emission sources and atmospheric processes. We conclude that N variability does not always reflect the impact of road traffic on air quality, whereas BC is a more consistent tracer of such ...

Abstract. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water), long-term tropospheric water vapour isotopologue data records are provided for ten globally distributed ground-based mid-infrared remote sensing stations of the NDACC (Network for the Detection of Atmospheric Composition Change). We present a new method allowing for an extensive and straightforward characterisation of the complex nature of such isotopologue remote sensing datasets. We demonstrate that the MUSICA humidity profiles are representative for most of the troposphere with a vertical resolution ranging from about 2 km (in the lower troposphere) to 8 km (in the upper troposphere) and with an estimated precision of better than 10 %. We find that the sensitivity with respect to the isotopologue composition is limited to the lower and middle troposphere, whereby we estimate a precision of about 30 ‰ for the ratio between the two isotopologues HD 16 O and H 16 2 O. The measurement noise, the applied atmospheric temperature profiles, the uncertainty in the spectral baseline, and the cross-dependence on humidity are the leading error sources. We introduce an a posteriori correction method of the cross-dependence on humidity, and we recommend applying it to isotopologue ratio remote sensing datasets in general. In addition, we present mid-infrared CO 2 retrievals and use them for demonstrating the MUSICA network-wide data consistency.In order to indicate the potential of long-term isotopologue remote sensing data if provided with a well-documented quality, we present a climatology and compare it to simulations of an isotope incorporated AGCM (Atmospheric General Circulation Model). We identify differences in the multiyear mean and seasonal cycles that significantly exceed the estimated errors, thereby indicating deficits in the modeled atmospheric water cycle.

Abstract. 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.

Abstract. In the lower/middle troposphere, {H 2 O,δD} pairs are good proxies for moisture pathways; however, their observation, in particular when using remote sensing techniques, is challenging. The project MUSICA (MUltiplatform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) addresses this challenge by integrating the remote sensing with in situ measurement techniques. The aim is to retrieve calibrated tropospheric {H 2 O,δD} pairs from the middle infrared spectra measured from ground by FTIR (Fourier transform infrared) spectrometers of the NDACC (Network for the Detection of Atmospheric Composition Change) and the thermal nadir spectra measured by IASI (Infrared Atmospheric Sounding Interferometer) aboard the MetOp satellites. In this paper, we present the final MUSICA products, and discuss the characteristics and potential of the NDACC/FTIR and MetOp/IASI {H 2 O,δD} data pairs.First, we briefly resume the particularities of an {H 2 O,δD} pair retrieval. Second, we show that the remote sensing data of the final product version are absolutely calibrated with respect to H 2 O and δD in situ profile references measured in the subtropics, between 0 and 7 km. Third, we reveal that the {H 2 O,δD} pair distributions obtained from the different remote sensors are consistent and allow distinct lower/middle tropospheric moisture pathways to be identified in agreement with multi-year in situ references. Fourth, we document the possibilities of the NDACC/FTIR instruments for climatological studies (due to long-term monitoring) and of the MetOp/IASI sensors for observing diurnal signals on a quasi-global scale and with high horizontal resolution. Fifth, we discuss the risk of misinterpreting {H 2 O,δD} pair distributions due to incomplete processing of the remote sensing products.

Abstract. This study investigates the long-term evolution of subtropical ozone profile time series (1999)(2000)(2001)(2002)(2003)(2004)(2005)(2006)(2007)(2008)(2009)(2010) obtained from ground-based FTIR (Fourier Transform InfraRed) spectrometry at the Izaña Observatory ozone super-site. Different ozone retrieval strategies are examined, analysing the influence of an additional temperature retrieval and different constraints. The theoretical assessment reveals that the FTIR system is able to resolve four independent ozone layers with a precision of better than 6 % in the troposphere and of better than 3 % in the lower, middle and upper stratosphere. This total error includes the smoothing error, which dominates the random error budget. Furthermore, we estimate that the measurement noise as well as uncertainties in the applied atmospheric temperature profiles and instrumental line shape are leading error sources. We show that a simultaneous temperature retrieval can significantly reduce the total random errors and that a regular determination of the instrumental line shape is important for producing a consistent long-term dataset. These theoretical precision estimates are empirically confirmed by daily intercomparisons with Electro Chemical Cell (ECC) sonde profiles. In order to empirically document the long-term stability of the FTIR ozone profile data we compare the linear trends and seasonal cycles as obtained from the FTIR and ECC time series. Concerning seasonality, in winter both techniques observe stratospheric ozone profiles that are typical middle latitude profiles (low tropopause, low ozone maximum concentrations) and in summer/autumn profiles that are typical tropical profiles (high tropopause, high maximum concentrations). The linear trends estimated from the FTIR and the ECC datasets agree within their error bars. For the FTIR time series, we observe a significant negative trend in the upper troposphere/lower stratosphere of about −0.2 % yr −1 and a significant positive trend in the middle and upper stratosphere of about +0.3 % yr −1 and +0.4 % yr −1 , respectively. Identifying such small trends is a difficult task for any measurement technique. In this context, super-sites applying different techniques are very important for the detection of reliable ozone trends.

Abstract. Within the project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) ground-and space-based remote sensing as well as in situ data sets of tropospheric water vapour isotopologues are provided. The space-based remote-sensing data set is produced from spectra measured by the IASI (Infrared Atmospheric Sounding Interferometer) sensor and is potentially available on a global scale.Here, we present the MUSICA IASI data for three different geophysical locations (subtropics, midlatitudes, and Arctic), and we provide a comprehensive characterisation of the complex nature of such space-based isotopologue remotesensing products. The quality assessment study is complemented by a comparison to MUSICA's ground-based FTIR (Fourier Transform InfraRed) remote-sensing data retrieved from the spectra recorded at three different locations within the framework of NDACC (Network for the Detection of Atmospheric Composition Change).We confirm that IASI is able to measure tropospheric H 2 O profiles with a vertical resolution of about 4 km and a random error of about 10 %. In addition IASI can observe middle tropospheric δD that adds complementary value to IASI's middle tropospheric H 2 O observations. Our study presents theoretical and empirical proof that IASI has the capability for a global observation of middle tropospheric water vapour isotopologues on a daily timescale and at a quality that is sufficiently high for water cycle research purposes.

Abstract. We present two years of in situ measurements of water vapour (H 2 O) and its isotopologue ratio (δD, the standardized ratio between H 2 16 O and HD 16 O), made at two remote mountain sites on Tenerife in the subtropical North Atlantic. We show that the data -if measured during night-time -are well representative for the lower/middle free troposphere. We use the measured H 2 O-δD pairs, together with dust measurements and back trajectory modelling for analysing the moisture pathways to this region. We can identify four principally different transport pathways. The air mass transport from high altitudes and high latitudes shows two different scenarios. The first scenario brings dry air masses to the stations, as the result of condensation events occurring at low temperatures. The second scenario brings humid air masses to the stations, due to cross-isentropic mixing with lower-level and more humid air during transport since last condensation (LC). The third pathway is transportation from lower latitudes and lower altitudes, whereby we can identify rain re-evaporation as an occasional source of moisture. The fourth pathway is linked to the African continent, where during summer, dry convection processes over the Sahara very effectively inject humidity from the boundary layer to higher altitudes. This so-called Saharan Air Layer (SAL) is then advected westward over the Atlantic and contributes to moisten the free troposphere. We demonstrate that the different pathways leave distinct fingerprints on the measured H 2 O-δD pairs.

Abstract. The project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) integrates tropospheric water vapour isotopologue remote sensing and in situ observations. This paper presents a first empirical validation of MUSICA's H 2 O and δD remote sensing products, generated from groundbased FTIR (Fourier transform infrared), spectrometer and space-based IASI (infrared atmospheric sounding interferometer) observation. The study is made in the area of the Canary Islands in the subtropical northern Atlantic. As reference we use well calibrated in situ measurements made aboard an aircraft (between 200 and 6800 m a.s.l.) by the dedicated ISOWAT instrument and on the island of Tenerife at two different altitudes (at Izaña, 2370 m a.s.l., and at Teide, 3550 m a.s.l.) by two commercial Picarro L2120-i water isotopologue analysers.The comparison to the ISOWAT profile measurements shows that the remote sensors can well capture the variations in the water vapour isotopologues, and the scatter with respect to the in situ references suggests a δD random uncertainty for the FTIR product of much better than 45 ‰ in the lower troposphere and of about 15 ‰ for the middle troposphere. For the middle tropospheric IASI δD product the study suggests a respective uncertainty of about 15 ‰. In both remote sensing data sets we find a positive δD bias of 30-70 ‰.Complementing H 2 O observations with δD data allows moisture transport studies that are not possible with H 2 O observations alone. We are able to qualitatively demonstrate the added value of the MUSICA δD remote sensing data. We document that the δD-H 2 O curves obtained from the different in situ and remote sensing data sets (ISOWAT, Picarro at Izaña and Teide, FTIR, and IASI) consistently identify two different moisture transport pathways to the subtropical north eastern Atlantic free troposphere.