ALBERT

Beschreibung: Measurements of organic marker compounds and inorganic species were performed on PM2.5 aerosols from a Belgian forest site that is severely impacted by urban pollution ("De Inslag", Brasschaat, Belgium) during a 2007 summer period within the framework of the "Formation mechanisms, marker compounds, and source apportionment for biogenic atmospheric aerosols (BIOSOL)" project. The measured organic species included (i) low-molecular weight (MW) dicarboxylic acids (LMW DCAs), (ii) methanesulfonate (MSA), (iii) terpenoic acids originating from the oxidation of α-pinene, β-pinene, d-limonene and Δ3-carene, and (iv) organosulfates related to secondary organic aerosol from the oxidation of isoprene and α-pinene. The organic tracers explained, on average, 5.3 % of the organic carbon (OC), of which 0.7 % was due to MSA, 3.4 % to LMW DCAs, 0.6 % to organosulfates, and 0.6 % to terpenoic acids. The highest atmospheric concentrations of most species were observed during the first five days of the campaign, which were characterised by maximum day-time temperatures 〉22 °C. Most of the terpenoic acids and the organosulfates peaked during day-time, consistent with their local photochemical origin. High concentrations of 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and low concentrations of cis-pinonic acid were noted during the first five days of the campaign, indicative of an aged biogenic aerosol. Several correlations between organic species were very high (r〉0.85), high (0.7

Beschreibung: In the lower/middle troposphere H2O-δD pairs are good proxies for moisture pathways, however their observation is challenging. The project MUSICA (MUlti-platform remote Sensing of Isotopologues for investigating the Cycle of Atmospheric water) addresses this challenge by integrating remote sensing with in-situ measurement techniques. The aim is to retrieve accurate tropospheric H2O-δD pairs from the middle infrared spectra measured from ground by the 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 review the MUSICA framework, present the final MUSICA products, and outline the NDACC/FTIR’s and METOP/IASI’s potential for observing accurate and consistent H2O-δD data pairs. First, we briefly resume the particularities of an H2O-δD pair retrieval. Second, we show that the remote sensing data of the final product version are absolutely calibrated with respect to H2O and δD in-situ profile references measured in the subtropics, between 0 and 7 km. Third, we empirically demonstrate that the calibrated remote sensing H2O-δD pairs can identify different lower/middle tropospheric moisture pathways and advert to the risk of misinterpretations caused by an incorrect processing of such remote sensing data. Fourth, we reveal that the different sensors (NDACC/FTIR instruments, MetOp/IASI-A, and MetOp/IASI-B) provide consistent H2O-δD pairs for very distinct atmospheric clear sky conditions. Fifth, we document the unique possibilities of the NDACC/FTIR instruments for providing long-term records (important for climatological studies) and of the MetOp/IASI sensors for observing diurnal signals on quasi global scale and with high horizontal resolution.

Beschreibung: 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.

Beschreibung: 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 an influence. However, N should be measured since ultrafine particles (

Beschreibung: 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? 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 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 an influence. The combination of PM10 and BC monitoring in urban areas potentially constitutes a useful approach to evaluate the impact of road traffic emissions on air quality.

Beschreibung: 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−), are assessed. A climatology of O3 transport pathways using backward trajectories shows that higher O3 values are associated with air masses traveling 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, but only for the summer-time. 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. At IZO 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.

Beschreibung: Measurements of organic marker compounds and inorganic species were performed on PM2.5 aerosols from a Belgian forest site that is severely impacted by urban pollution ("De Inslag", Brasschaat, Belgium) during a 2007 summer period within the framework of the "Formation mechanisms, marker compounds, and source apportionment for biogenic atmospheric aerosols (BIOSOL)" project. The objectives of this study were to determine sources, source processes, time series, and diel variations of the organic species, and to explore the relationships between their concentrations and those of trace gases (O3, NO2, SO2, and CO2) or meteorological parameters (temperature, relative humidity, wind speed, and rain fall). The measured organic species included (i) low-molecular weight (MW) dicarboxylic acids (LMW DCAs), (ii) methanesulfonate (MSA), and (iii) terpenoic acids originating from the oxidation of α-pinene, β-pinene, d-limonene and Δ3-carene, and (iv) organosulfates related to secondary organic aerosol (SOA) from the oxidation of isoprene and α-pinene. The measurements of MSA, the LMW DCAs and selected inorganic species were done with ion chromatography (IC), while those of the terpenoic acids and organosulfates were performed using liquid chromatography with negative ion electrospray ionisation mass spectrometry [LC/(−)ESI-MS]. The organic tracers explained, on average, 5.3 % of the organic carbon (OC), of which 0.7 % was due to MSA, 3.4 % to LMW DCAs, and 1.2 % to organosulfates and terpenoic acids. The highest atmospheric concentrations of most species were observed during the first five days of the campaign, which were characterised by maximum day-time temperatures 〉22 °C. Most of the terpenoic acids and the organosulfates peaked during day-time, consistent with their photochemical origin, except the MW 295 α-pinene-related nitrooxy organosulfates and the terpenoic acids, cis-pinic, caric, and limonic acid. High concentrations of 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) and low concentrations of cis-pinonic acid were noted during the first five days of the campaign, indicative of an aged biogenic aerosol. Several correlations between organic species were very high (r〉0.85), high (0.7

Beschreibung: A climatology of new particle formation (NPF) events in the subtropical North Atlantic free troposphere is presented. A four year data set (June 2008–June 2012), which includes number size distributions (10–600 nm), reactive gases (SO2, NOx, and O3), several components of solar radiation and meteorological parameters, measured at Izaña Global Atmospheric Watch observatory (2400 m above sea level; Tenerife, Canary Islands) was analysed. On average, NPF occurred during 30% of the days,the mean values of the formation and growth rates during the study period were 0.49 cm−3 s−1 and 0.42 nm h−1, correspondingly. There is a clearly marked NPF season (May to August), when these events account for 50 to 60% of the days/month. Monthly mean values of the formation and growth rates exhibit higher values during this season (0.50–0.95 cm−3 s−1 and 0.48–0.58 nm h−1, respectively) than during other periods. The two steps (formation and growth) of the NPF process mostly occur under the prevailing northern winds typical of this region. Sulphur dioxide and UV radiation show higher levels during NPF events than in other type of episodes. The presence of Saharan dust in the free troposphere is associated with a decrease in the formation rates of new particles. In the analysis of the year-to-year variability, mean sulphur dioxide concentration (within the range 60–300 ppt) was the parameter that exhibited the highest correlation with the frequency of NPF episodes. The availability of this trace gas (i.e. their oxidation products) seems also to have a influence on the duration of the events, number of formed nucleation particles, formation rates and growth rates. We identified a set of NPF events in which two nucleation modes (that may evolve at different rates) occur simultaneously and for which further investigations are necessary.

Beschreibung: We present two years of measurements of water vapour (H2O) and its isotopologue ratio (δD, the standardized ratio between H216O and HD16O) made at two remote mountain sites on Tenerife Island in the subtropical North Atlantic. We show that the data – if measured during nighttime – are well representative for the lower/middle free troposphere. We use the measured H2O-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 first two pathways are linked to transport from high altitudes and high latitudes, whereby the respective air can be dry, due to last condensation occurring at low temperatures, as well as humid, due to cross isentropic mixing with lower level and more humid air during transport since last condensation. The third pathway is transport 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 different pathways leave distinct fingerprints on the measured H2O-δD pairs.

Beschreibung: We investigate the long-term evolution of subtropical ozone profile time series (1999–2010) obtained from different ground-based FTIR (Fourier Transform InfraRed) retrieval setups. We examine the influence of an additional temperature retrieval and different constraints. The study is performed at the Izaña Observatory ozone super-site (Tenerife Island, Spain). The FTIR system is able to resolve four independent ozone layers with a theoretical precision of better than 7.5% in the troposphere, lower, middle and upper stratosphere. This total error includes the smoothing error, which is dominating the random error budget. Furthermore, our theoretical calculations indicate that a very precise knowledge of the instrumental line shape is mandatory for a precise ground-based FTIR remote sensing of stratospheric ozone. Likewise, we show that a simultaneous temperature retrieval is highly recommended. We empirically confirm our precision estimates by daily intercomparisons with Electro Chemical Cell (ECC) sonde profiles. Both FTIR and ECC sonde profile time series show similar seasonality: in winter stratospheric ozone profiles are typical middle latitude profiles (low tropopause, low ozone maximum concentrations) and in summer/autumn they are typical tropical profiles (high tropopause, high maximum concentrations). Good agreement is also observed for the linear trends estimated from the FTIR and the ECC datasets: a negative trend in the upper troposphere/lower stratosphere region of about −0.3% yr−1 and a positive trend in the middle/upper stratosphere of about +0.3% yr−1. Admittedly, a 12-yr time series is too short for reliable trend studies, however, it is worthwhile mentioning that such subtropical ozone profile trends are predicted by climate models due to an increased stratospheric circulation in response to climate change.