Index Geophysics

Items

• Characterization of aerosol and cloud water at a mountain site during WACS 2010: secondary organic aerosol formation through oxidative cloud processing

  The water-soluble fractions of aerosol filter samples and cloud water collected during the Whistler Aerosol and Cloud Study (WACS 2010) were analyzed using an Aerodyne aerosol mass spectrometer (AMS). This is the first study to report AMS organic spectra of re-aerosolized cloud water, and to make direct comparison between the AMS spectra of cloud water and aerosol samples collected at the same location. In general, the mass spectra of aerosol were very similar to those of less volatile cloud organics. By using a photochemical reactor to oxidize both aerosol filter extracts and cloud water, we find evidence that fragmentation of water-soluble organics in aerosol increases their volatility during photochemical oxidation. By contrast, enhancement of AMS-measurable organic mass by up to 30% was observed during the initial stage of oxidation of cloud water organics, which was followed by a decline at the later stages of oxidation. These observations are in support of the general hypothesis that cloud water oxidation is a viable route for SOA formation. In particular, we propose that additional SOA material was produced by functionalizing dissolved organics via OH oxidation, where these dissolved organics are sufficiently volatile that they are not usually part of the aerosol. This work demonstrates that water-soluble organic compounds of intermediate volatility (IVOC), such as <i>cis</i>-pinonic acid, produced via gas-phase oxidation of monoterpenes, can be important aqueous-phase SOA precursors in a biogenic-rich environment.

• French airborne lidar measurements for Eyjafjallajökull ash plume survey

  An Ultra-Violet Rayleigh-Mie lidar has been integrated aboard the French research aircraft Falcon20 in order to monitor the ash plume emitted by the Eyjafjallajökul volcano in April–May 2010. Three operational flights were carried out on 21 April, 12 and 16 May 2010 inside French, Spanish and British air spaces, respectively. The original purpose of the flights was to provide the French civil aviation authorities with objective information on the presence and location of the ash plume. The present paper presents the results of detailed analyses elaborated after the volcano crisis. They bear on the structure of the ash clouds and their optical properties such as the extinction coefficient and the lidar ratio. Lidar ratios were measured in the range of 43 to 50 sr, in good agreement with the ratios derived from ground-based lidar near Paris (France) in April 2010 (~48 sr). The ash signature in terms of particulate depolarization was consistent during all flights (between 34 ± 3 % and 38 ± 3%). Such a value seems to be a good identification parameter for volcanic ash. Using specific cross-sections between 0.19 and 1.1 m² g^&minus;1, the minimum (maximal) mass concentrations in the ash plumes derived for the flights on 12 and 16 May were 140 (2300) and 250 (1500) &mu;g m^&minus;3, respectively. It may be rather less than, or of the order of the critical level of damage (2 mg m^&minus;3) for the aircraft engines, but well above the 200 &mu;g m⁻³ warning level.

• The direct effect of aerosols on solar radiation over the broader Mediterranean basin

  For the first time, the direct radiative effect (DRE) of aerosols on solar radiation is computed over the entire Mediterranean basin, one of the most climatically sensitive world regions, using a deterministic spectral radiation transfer model (RTM). The DRE effects on the outgoing shortwave radiation at the top of atmosphere (TOA), DRE_TOA, on the absorption of solar radiation in the atmospheric column, DRE_atm, and on the downward and absorbed surface solar radiation (SSR), DRE_surf and DRE_netsurf, respectively, are computed separately. The model uses input data for the period 2000–2007 for various surface and atmospheric parameters, taken from satellite (International Satellite Cloud Climatology Project, ISCCP-D2), Global Reanalysis projects (National Centers for Environmental Prediction – National Center for Atmospheric Research, NCEP/NCAR), and other global databases. The spectral aerosol optical properties (aerosol optical depth, AOD, asymmetry parameter, <i>g</i>_aer and single scattering albedo, &omega;_aer), are taken from the MODerate resolution Imaging Spectroradiometer (MODIS) of NASA (National Aeronautics and Space Administration) and they are supplemented by the Global Aerosol Data Set (GADS). The model SSR fluxes have been successfully validated against measurements from 80 surface stations of the Global Energy Balance Archive (GEBA) covering the period 2000–2007. <br><br> A planetary cooling is found above the Mediterranean on an annual basis (regional mean DRE_TOA = &minus;2.4 W m⁻²). Although a planetary cooling is found over most of the region, of up to −7 W m⁻², large positive DRE_TOA values (up to +25 W m⁻²) are found over North Africa, indicating a strong planetary warming, and a weaker warming over the Alps (+0.5 W m⁻²). Aerosols are found to increase the absorption of solar radiation in the atmospheric column over the region (DRE_atm = +11.1 W m⁻²) and to decrease SSR (DRE_surf = &minus;16.5 W m⁻² and DRE_netsurf&minus;13.5 W m⁻²) inducing thus significant atmospheric warming and surface radiative cooling. The calculated seasonal and monthly DREs are even larger, reaching −25.4 W m⁻² (for DRE_surf). Within the range of observed natural or anthropogenic variability of aerosol optical properties, AOD seems to be the main responsible parameter for modifications of regional aerosol radiative effects, which are found to be quasi-linearly dependent on AOD, &omega;_aer and <i>g</i>_aer.

• Fast cloud parameter retrievals of MIPAS/Envisat

  The infrared limb spectra of the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on board the Envisat satellite include detailed information on tropospheric clouds and polar stratospheric clouds (PSC). However, no consolidated cloud product is available for the scientific community. Here we describe a fast prototype processor for cloud parameter retrieval from MIPAS (MIPclouds). Retrieval of parameters such as cloud top height, temperature, and extinction are implemented, as well as retrieval of microphysical parameters, e.g. effective radius and the integrated quantities over the limb path (surface area density and volume density). MIPclouds classifies clouds as either liquid or ice cloud in the upper troposphere and polar stratospheric clouds types in the stratosphere based on statistical combinations of colour ratios and brightness temperature differences. <br><br> Comparison of limb measurements of clouds with model results or cloud parameters from nadir looking instruments is often difficult due to different observation geometries. We therefore introduce a new concept, the limb-integrated surface area density path (ADP). By means of validation and radiative transfer calculations of realistic 2-D cloud fields as input for a blind test retrieval (BTR), we demonstrate that ADP is an extremely valuable parameter for future comparison with model data of ice water content, when applying limb integration (ray tracing) through the model fields. In addition, ADP is used for a more objective definition of detection thresholds of the applied detection methods. Based on BTR, a detection threshold of ADP = 10⁷ μm² cm⁻² and an ice water content of 10^&minus;5 g m⁻³ is estimated, depending on the horizontal and vertical extent of the cloud. <br><br> Intensive validation of the cloud detection methods shows that the limb-sounding MIPAS instrument has a sensitivity in detecting stratospheric and tropospheric clouds similar to that of space- and ground-based lidars, with a tendency for higher cloud top heights and consequently higher sensitivity for some of the MIPAS detection methods. For the high cloud amount (HCA, pressure levels below 440 hPa) on global scales the sensitivity of MIPAS is significantly greater than that of passive nadir viewers. This means that the high cloud fraction will be underestimated in the ISCCP dataset compared to the amount of high clouds deduced by MIPAS. Good correspondence in seasonal variability and geographical distribution of cloud occurrence and zonal means of cloud top height is found in a detailed comparison with a climatology for subvisible cirrus clouds from the Stratospheric Aerosol and Gas Experiment II (SAGE II) limb sounder. Overall, validation with various sensors shows the need to consider differences in sensitivity, and especially the viewing geometries and field-of-view size, to make the datasets comparable (e.g. applying integration along the limb path through nadir cloud fields). The simulation of the limb path integration will be an important issue for comparisons with cloud-resolving global circulation or chemical transport models.

• Direct and disequilibrium effects on precipitation in transient climates

  Climate models are in broad agreement that global precipitation increases with surface temperature as atmospheric CO₂ concentrations rise, but recent studies have shown that climates that are not yet in equilibrium exhibit additional "transient precipitation effects". In conditions of rising CO₂, for example, precipitation at a given temperature is suppressed relative to its equilibrium value. Some authors argue that the primary driver of these effects is ocean heat uptake, but most recent studies assume that they result from some direct radiative effect. We show here that global precipitation and temperature anomalies are insufficient to resolve mechanisms, since the conventional "fast/slow" representation of transient precipitation effects is degenerate with a "disequilibrium" representation that posits control only by ocean heat uptake. We use regional anomalies instead to show in multiple ways that ocean heat uptake is the dominant driver of transient precipitation effects in CO₂-forced climates. Precipitation suppression appears predominantly over the ocean, with response over land of the opposite sign. The coefficients of a disequilibrium representation are uncorrelated, suggesting that they capture physically meaningful processes, while those of a fast/slow representation are highly correlated. Further, the regional patterns of transient precipitation response are highly similar for both CO₂ and solar forcing, with a relatively small and homogeneous offset between them. Examination of the surface energy budget allows us to conclude that energy balance in solar-forced climates is achieved by the superposition of both disequilibrium and direct processes. Our results highlight the importance of using regional information rather than global aggregates for understanding the physics of transient climate change and its impacts on societies.

• Upwelling into the lower stratosphere forced by breaking tropical waves: evidence from chemical tracers

  Measurements from the Microwave Limb Sounder (MLS) on the 68 hPa pressure level from 1 January 2005 to 31 December 2010 are used to calculate the coherence between anomalies in the tropical mean mixing ratios of H₂O, CO, and N₂O, and 100 hPa temperature. We show that the fluctuations of lower stratospheric water vapor in the subseasonal and multiyear time windows are generated by different physical mechanisms. In the subseasonal time window, the spatial pattern of the coherence between 100 hPa temperature and water vapor, and the time lag, show that the variability in lower stratospheric water vapor is dominated by fluctuations in upwelling forced by the dissipation of tropical Rossby waves. In the multiyear time window, the variability of lower stratospheric water vapor is more strongly coherent with temperature fluctuations on the 100 hPa surface in regions where the annual mean temperature is colder than 194 K. In addition, the 68 hPa water vapor anomalies lag the 100 hPa temperature anomalies by roughly 140 days. In this time window, the variability of lower stratospheric water vapor is therefore dominated by changes in the temperature dependent dehydration efficiency which modulate the water vapor stratospheric entry mixing ratio. On subseasonal timescales, the spatial pattern of the coherence between 100 hPa temperature and 68 hPa CO anomalies is very similar to the pattern of coherence between 100 hPa temperature and the Real-time Multivariate MJO series 1 (RMM1) index of the Madden Julian Oscillation (MJO). The MJO therefore has a strong influence on the subseasonal variability of CO in the lower stratosphere. The subseasonal 68 hPa CO and H₂O anomalies lag the 100 hPa temperature anomalies by 3.16 and 2.51 days, respectively. The similarity between the two time lags suggests that the subseasonal CO anomalies can also be attributed to changes in upwelling. The multiyear variability in lower stratospheric N₂O appears to be dominated by the Quasi Biennial Oscillation (QBO).

• Understanding the aqueous phase ozonolysis of isoprene: distinct product distribution and mechanism from the gas phase reaction

  The aqueous phase reaction of volatile organic compounds (VOCs) has not been considered in most analyses of atmospheric chemical processes. However, some experimental evidence has shown that, compared to the corresponding gas phase reaction, the aqueous chemical processes of VOCs in the bulk solutions and surfaces of ambient wet particles (cloud, fog, and wet aerosols) may potentially contribute to the products and formation of secondary organic aerosol (SOA). In the present study, we performed a laboratory experiment of the aqueous ozonolysis of isoprene at different pHs (3–7) and temperatures (4–25 °C). We detected three important kinds of products, including carbonyl compounds, peroxide compounds, and organic acids. Our results showed that the molar yields of these products were nearly independent of the investigated pHs and temperatures, those were (1) carbonyls: 56.7 ± 3.7 % formaldehyde, 42.8 ± 2.5 % methacrolein (MAC), and 57.7 ± 3.4 % methyl vinyl ketone (MVK); (2) peroxides: 53.4 ± 4.1 % hydrogen peroxide (H₂O₂) and 15.1 ± 3.1 % hydroxylmethyl hydroperoxide (HMHP); and (3) organic acids: undetectable (<1 % estimated by the detection limit). Based on the amounts of products formed and the isoprene consumed, the total carbon yield was estimated to be 94.8 ± 4.1 %. This implied that most of the products in the reaction system were detected. The combined yields of both MAC + MVK and H₂O₂ + HMHP in the aqueous isoprene ozonolysis were much higher than those observed in the corresponding gas phase reaction. We suggest that these unexpected high yields of carbonyls and peroxides are related to the greater capability of condensed water, compared to water vapor, to stabilize energy-rich Criegee radicals. This aqueous ozonolysis of isoprene (and possibly other biogenic VOCs) could potentially occur on the surfaces of ambient wet particles and plants. Moreover, the high-yield carbonyl and peroxide products might provide a considerable source of aqueous phase oxidants and SOA precursors.

• Diel cycles of isoprenoids in the emissions of Norway spruce, four Scots pine chemotypes, and in Boreal forest ambient air during HUMPPA-COPEC-2010

  Branch enclosure based emission rates of monoterpenes and sesquiterpenes from four Scots pines (<i>Pinus sylvestris</i>) and one Norway spruce (<i>Picea abies</i>), as well as the ambient mixing ratios of monoterpenes were determined during the HUMPPA-COPEC 2010 summer campaign. Differences in chemical composition and in emission strength were observed between the different trees, which confirmed that they represented different chemotypes. The chemotypes of Scots pine can be classified according to species with high, no and intermediate content of Δ-3-carene. The "non-Δ-3-carene" chemotype was found to be the strongest emitter of monoterpenes. From this chemotype, β-myrcene, a very reactive monoterpene, was the dominant species accounting for more than 32 % of the total emission rates of isoprenoids followed by β-phellandrene (~27%). Myrcene fluxes ranged from 0.8 to 24 μg g⁻¹ (dw) h⁻¹. α-Farnesene was the dominant sesquiterpene species, with average emission rates of 318 ng g⁻¹ (dw) h⁻¹. In the high Δ-3-carene chemotype, more than 48% of the total monoterpene emission was Δ-3-carene. The average Δ-3-carene emission rate (from chemotype 3), circa 609 ng g⁻¹ (dw) h⁻¹ reported here is consistent with the previously reported summer season value. Daily maximum temperatures varied between 20 and 35 °C during the measurements. The monoterpene emissions from spruce were dominated by limonene (35%), β-phellandrene (15%), α-pinene (14%) and eucalyptol (9%). Total spruce monoterpene emissions ranged from 0.55 up to 12.2 μg g⁻¹ (dw) h⁻¹. Overall the total terpene flux (monoterpenes + sesquiterpenes) from all studied tree species varied from 230 ng g⁻¹ (dw) h⁻¹ up to 66 μg g⁻¹ (dw) h⁻¹. Total ambient monoterpenes (including α-pinene, Δ-3-carene, β-pinene and β-myrcene) measured during the campaign varied in mixing ratio from a few pptv to over one ppbv. The most abundant biogenic VOC measured above the canopy were α-pinene and Δ-3-carene, and these two compounds together contributed more than 50% of the total monoterpenes. The ambient data reflect the emission rate, atmospheric reactivity and tree type abundance. The diel cycles of isoprenoid mixing ratios showed high levels during the night-time which is consistent with continued low nocturnal emission and a low and stable boundary layer. The chirality of α-pinene was dominated by (+)-enantiomers both in the direct emission and in the atmosphere. The two highest emitters showed no enantiomeric preference for α-pinene emissions, whereas the two lowest emitting pines emitted more (+)-enantiomer. The spruce emissions were dominated by (−)-enantiomer. The exceptionally hot temperatures in the summer of 2010 led to relatively strong emissions of monoterpenes, greater diversity in chemical composition and high ambient mixing ratios.

• Spatial variation of aerosol optical properties around the high-alpine site Jungfraujoch (3580 m a.s.l.)

  This paper presents results of the extensive field campaign CLACE 2010 (Cloud and Aerosol Characterization Experiment) performed in summer 2010 at the Jungfraujoch (JFJ) and the Kleine Scheidegg (KLS) in the Swiss Alps. The main goal of this campaign was to investigate the vertical variability of aerosol optical properties around the JFJ and to show the consistency of the different employed measurement techniques considering explicitly the effects of relative humidity (RH) on the aerosol light scattering. Various aerosol optical and microphysical parameters were recorded using in-situ and remote sensing techniques. In-situ measurements of aerosol size distribution, light scattering, light absorption and scattering enhancement due to water uptake were performed at the JFJ at 3580 m a.s.l.. A unique set-up allowed remote sensing measurements of aerosol columnar and vertical properties from the KLS located about 1500 m below and within the line of sight to the JFJ (horizontal distance of approx. 4.5 km). In addition, two satellite retrievals from the Spinning Enhanced Visible and Infrared Imager (SEVIRI) and the Moderate Resolution Imaging Spectroradiometer (MODIS) as well as back trajectory analyses were added to the comparison to account for a wider geographical context. All in-situ and remote sensing measurements were in clear correspondence. The ambient extinction coefficient measured in situ at the JFJ agreed well with the KLS-based LIDAR (Light Detection and Ranging) retrieval at the altitude-level of the JFJ under plausible assumptions on the LIDAR ratio. However, we can show that the quality of this comparison is affected by orographic effects due to the exposed location of the JFJ on a saddle between two mountains and next to a large glacier. The local RH around the JFJ was often higher than in the optical path of the LIDAR measurement, especially when the wind originated from the south via the glacier, leading to orographic clouds which remained lower than the LIDAR beam. Furthermore, the dominance of long-range transported Saharan dust was observed in all measurements for several days, however only for a shorter time period in the in-situ measurements due to the vertical structure of the dust plume. The optical properties of the aerosol column retrieved from SEVIRI and MODIS showed the same magnitude and a similar temporal evolution as the measurements at the KLS and the JFJ. Remaining differences are attributed to the complex terrain and simplifications in the aerosol retrieval scheme in general.

• Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements

  In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s⁻¹; range of average diel values: 21.3–40.5 s⁻¹), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s⁻¹; range of average diel values: 7–23.4 s⁻¹) and marine air masses (average: 6.3 ± 6.6 s⁻¹; range of average diel values: below detection limit −21.7 s⁻¹), respectively. The average OH reactivity for the entire campaign period was ~18 s⁻¹ and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NO_x with peak values of around 20 ppbV O₃ h⁻¹. Using the OH reactivity based approach, derived ozone production rates indicate that if NO_x would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.