ALBERT

Beschreibung: Hydroxyl radical buffered by isoprene oxidation over tropical forests Nature Geoscience 5, 190 (2012). doi:10.1038/ngeo1405 Authors: D. Taraborrelli, M. G. Lawrence, J. N. Crowley, T. J. Dillon, S. Gromov, C. B. M. Groß, L. Vereecken & J. Lelieveld The hydroxyl radical is a key oxidant in the Earth’s atmosphere. This short-lived highly reactive molecule plays an important role in the degradation of volatile organic compounds, leading to the production of ozone and the formation and growth of aerosol particles. In this way, hydroxyl radicals influence air quality and regional climate. Measurements over tropical forests suggest that hydroxyl radicals are recycled following reaction with the volatile organic compound isoprene, but the chemistry underpinning this observation is uncertain. Here, we propose a detailed chemical mechanism for the oxidation of isoprene by hydroxyl radicals. The photo-oxidation of unsaturated hydroperoxy-aldehydes—a product of isoprene oxidation—is a central part of the mechanism; their photolysis initiates a hydroxyl radical production cascade that is limited by the reaction of hydroperoxy-aldehydes with the hydroxyl radical itself. We incorporate this mechanism into a global atmospheric chemistry model and find that measurements of hydroxyl radical concentrations over a pristine region of the Amazon, and in moderately polluted conditions, are captured well. On the basis of this agreement, we suggest that isoprene oxidation can buffer hydroxyl radical concentrations, by serving as both a sink and source for these radicals.

Beschreibung: Hydroxyl radical buffered by isoprene oxidation over tropical forests Nature Geoscience 5, 300 (2012). doi:10.1038/ngeo1433 Authors: D. Taraborrelli, M. G. Lawrence, J. N. Crowley, T. J. Dillon, S. Gromov, C. B. M. Groß, L. Vereecken & J. Lelieveld

Beschreibung: As a contribution to the Large-Scale Biosphere-Atmosphere Experiment in Amazonia – Cooperative LBA Airborne Regional Experiment (LBA-CLAIRE-2001) field campaign in the heart of the Amazon Basin, we analyzed the temporal and spatial dynamics of the urban plume of Manaus City during the wet-to-dry season transition period in July 2001. During the flights, we performed vertical stacks of crosswind transects in the urban outflow downwind of Manaus City, measuring a comprehensive set of trace constituents including O3, NO, NO2, CO, VOC, CO2, and H2O. Aerosol loads were characterized by total aerosol number concentration (CN) and cloud condensation nuclei (CCN) concentrations, and light scattering properties. Measurements over pristine rainforest areas during the campaign showed low levels of pollution from biomass burning or industrial emissions, representative of wet season background conditions. The urban plume of Manaus City was found to be joined by plumes from power plants south of the city, all showing evidence of very strong photochemical ozone formation. One episode is discussed in detail, where a threefold increase in ozone mixing ratios in the atmospheric boundary layer occurred within a 100 km travel distance downwind of Manaus. Observation-based estimates of the ozone production rates in the plume reached 15 ppb h−1. Within the plume core, aerosol concentrations were strongly enhanced, with ΔCN/ΔCO ratios about one order of magnitude higher than observed in Amazon biomass burning plumes. ΔCN/ΔCO ratios tended to decrease with increasing transport time, indicative of a significant reduction in particle number by coagulation, and without substantial new particle nucleation occurring within the time/space observed. While in the background atmosphere a large fraction of the total particle number served as CCN (about 60–80% at 0.6% supersaturation), the CCN/CN ratios within the plume indicated that only a small fraction (16 ± 12%) of the plume particles were CCN. The fresh plume aerosols showed relatively weak light scattering efficiency. The CO-normalized CCN concentrations and light scattering coefficients increased with plume age in most cases, suggesting particle growth by condensation of soluble organic or inorganic species. We used a Single Column Chemistry and Transport Model (SCM) to infer the urban pollution emission fluxes of Manaus City, implying observed mixing ratios of CO, NOx and VOC. The model can reproduce the temporal/spatial distribution of ozone enhancements in the Manaus plume, both with and without accounting for the distinct (high NOx) contribution by the power plants; this way examining the sensitivity of ozone production to changes in the emission rates of NOx. The VOC reactivity in the Manaus region was dominated by a high burden of biogenic isoprene from the background rainforest atmosphere, and therefore NOx control is assumed to be the most effective ozone abatement strategy. Both observations and models show that the agglomeration of NOx emission sources, like power plants, in a well-arranged area can decrease the ozone production efficiency in the near field of the urban populated cores. But on the other hand remote areas downwind of the city then bear the brunt, being exposed to increased ozone production and N-deposition. The simulated maximum stomatal ozone uptake fluxes were 4 nmol m−2 s−1 close to Manaus, and decreased only to about 2 nmol m−2 s−1 within a travel distance 〉1500 km downwind from Manaus, clearly exceeding the critical threshold level for broadleaf trees. Likewise, the simulated N deposition close to Manaus was ~70 kg N ha−1 a−1 decreasing only to about 30 kg N ha−1 a−1 after three days of simulation.

Beschreibung: As a major source region of the hydroxyl radical OH, the Tropics largely control the oxidation capacity of the atmosphere on a global scale. However, emissions of hydrocarbons from the tropical rainforest that react rapidly with OH can potentially deplete the amount of OH and thereby reduce the oxidation capacity. The airborne GABRIEL field campaign in equatorial South America (Suriname) in October 2005 investigated the influence of the tropical rainforest on the HOx budget (HOx = OH + HO2). The first observations of OH and HO2 over a tropical rainforest are compared to steady state concentrations calculated with the atmospheric chemistry box model MECCA. The important precursors and sinks for HOx chemistry, measured during the campaign, are used as constraining parameters for the simulation of OH and HO2. Significant underestimations of HOx are found by the model over land during the afternoon, with mean ratios of observation to model of 12.2 ± 3.5 and 4.1 ± 1.4 for OH and HO2, respectively. The discrepancy between measurements and simulation results is correlated to the abundance of isoprene. While for low isoprene mixing ratios (above ocean or at altitudes 〉3 km), observation and simulation agree fairly well, for mixing ratios 〉200 pptV (

Beschreibung: Ozone (O3) is a photochemical oxidant, an air pollutant and a greenhouse gas. As the main precursor of the hydroxyl radical (OH) it strongly affects the oxidation power of the atmosphere. The remote marine boundary layer (MBL) is considered an important region in terms of chemical O3 loss; however surface-based atmospheric observations are sparse and the photochemical processes are not well understood. To investigate the photochemistry under the clean background conditions of the Southern Atlantic Ocean, ship measurements of NO, NO2, O3, JNO2, J(O1D), HO2, OH, ROx and a range of meteorological parameters were carried out. The concentrations of NO and NO2 measured on board the French research vessel Marion-Dufresne (28° S–57° S, 46° W–34° E) in March 2007, are among the lowest yet observed. The data is evaluated for consistency with photochemical steady state (PSS) conditions, and the calculations indicate substantial deviations from PSS (Φ〉1). The deviations observed under low NOx conditions (5–25 pptv) demonstrate a remarkable upward tendency in the Leighton ratio (used to characterize PSS) with increasing NOx mixing ratio and JNO2 intensity. It is a paradigm in atmospheric chemistry that OH largely controls the oxidation efficiency of the atmosphere. However, evidence is growing that for unpolluted low-NOx (NO + NO2) conditions the atmospheric oxidant budget is poorly understood. Nevertheless, for the very cleanest conditions, typical for the remote marine boundary layer, good model agreement with measured OH and HO2 radicals has been interpreted as accurate understanding of baseline photochemistry. Here we show that such agreement can be deceptive and that a yet unidentified oxidant is needed to explain the photochemical conditions observed at 40°–60° S over the Atlantic Ocean.

Beschreibung: We present a numerical modelling study investigating the impact of mineral dust on cloud formation over the Eastern Mediterranean for two case studies: (i) 25 September 2008 and (ii) 28/29 January 2003. In both cases dust plumes crossed the Mediterranean and interacted with clouds forming along frontal systems. For our investigation we used the fully online coupled model WRF-chem. The results show that increased aerosol concentrations due to the presence of mineral dust can enhance the formation of ice crystals. This leads to slight shifts of the spatial and temporal precipitation patterns compared to scenarios where dust was not considered to act as ice nuclei. However, the total amount of precipitation did not change significantly. The only exception occurred when dust entered into an area of orographic ascent, causing glaciation of the clouds, leading to a local enhancement of rainfall. The impact of dust particles acting as giant cloud condensation nuclei on precipitation formation was found to be small. Based on our simulations the contribution of dust to the CCN population is potentially significant only for warm phase clouds. Nevertheless, the dust-induced differences in the microphysical structure of the clouds can contribute to a significant radiative forcing, which is important from a climate perspective.

Beschreibung: We studied the atmospheric boundary layer (ABL) dynamics and the impact on atmospheric chemistry during the HUMPPA-COPEC-2010 campaign. We used vertical profiles of potential temperature and specific moisture, obtained from 132 radio soundings, to determine the main boundary layer characteristics during the campaign. We propose a classification according to several main ABL prototypes. Further, we performed a case study of a single day, focusing on the convective boundary layer, to analyse the influence of the dynamics on the chemical evolution of the ABL. We used a mixed layer model, initialized and constrained by observations. In particular, we investigated the role of large scale atmospheric dynamics (subsidence and advection) on the ABL development and the evolution of chemical species concentrations. We find that, if the large scale forcings are taken into account, the ABL dynamics are represented satisfactorily. Subsequently, we studied the impact of mixing with a residual layer aloft during the morning transition on atmospheric chemistry. The time evolution of NOx and O3 concentrations, including morning peaks, can be explained and accurately simulated by incorporating the transition of the ABL dynamics from night to day. We demonstrate the importance of the ABL height evolution for the representation of atmospheric chemistry. Our findings underscore the need to couple the dynamics and chemistry at different spatial scales (from turbulence to mesoscale) in chemistry-transport models and in the interpretation of observational data.

Beschreibung: Recent theoretical calculations showed that reaction with HO2 could be an important sink for acetone (CH3C(O)CH3) and source of acetic acid (CH3C(O)OH) in cold parts of the atmosphere (e.g. the tropopause region). This work details studies of HO2 + CH3C(O)CH3 (CH3)2C(OH)OO (R1) in laboratory-based and theoretical chemistry experiments; the atmospheric significance of Reaction (R1) was assessed in a global 3-D chemical model. Pulsed laser-kinetic experiments were conducted, for the first time, at the low-temperatures representative of the tropopause. Reaction with NO converted HO2 to OH for detection by laser induced fluorescence. Reduced yields of OH at T 〈 220 K provided indirect evidence for the sequestration of HO2 by CH3C(O)CH3 with a forward rate coefficient greater than 2 × 10−12 cm3 molecule−1 s−1. No evidence for Reaction (R1) was observed at T 〉 230 K, probably due to rapid thermal dissociation back to HO2 + CH3C(O)CH3. Numerical simulations of the data indicate that these experiments were sensitive to only (R1a) HO2-CH3C(O)CH3 complex formation, the first step in (R1). Rearrangement (R1b) of the complex to form peroxy radicals, and hence the atmospheric significance of (R1) has yet to be rigorously verified by experiment. Results from new quantum chemical calculations indicate that K1 is characterised by large uncertainties of at least an order of magnitude at T 〈 220 K. The large predicted values from Hermans et al. lie at the top end of the range of values obtained from calculations at different (higher) levels of theory. Atmospheric modelling studies demonstrated that whilst (R1) chemistry may be a significant loss process for CH3C(O)CH3 near the tropopause, it cannot explain observations of CH3C(O)OH throughout the troposphere.

Beschreibung: We examined the influence of the North Atlantic Oscillation (NAO) on the atmospheric dispersion of pollution by computing the emission, transport and removal of idealized insoluble gaseous and water-soluble aerosol tracers, tagged by the continent of origin. We simulated a period of 50 yr (1960–2010), using the ECHAM5/MESSy1 atmospheric chemistry (EMAC) general circulation model. The model accounts for anthropogenic, biogenic and biomass burning sources, removal of trace gases through OH oxidation, and precipitation, sedimentation and deposition of aerosols. The model is shown to reproduce the observed spatial features of the NAO, moisture transports and precipitation. During high NAO phase seasons the axis of maximum westerly North American trace gas transports extends relatively far to the north and east over Europe. The NAO phase is significantly correlated with North American insoluble gas and soluble aerosol tracer concentrations over the northwestern Atlantic Ocean and across northern Europe, and with European trace gases and aerosols over Africa and north of the Arctic circle. We find a strong anti-correlation between the phase of the NAO and European pollutant gas concentration over western and central Europe.