Index Geophysics

Items

• Simulation of denitrification and ozone loss for the Arctic winter 2002/2003

  We present simulations with the Chemical Lagrangian Model of the Stratosphere (CLaMS) for the Arctic winter 2002/2003. We integrated a Lagrangian denitrification scheme into the three-dimensional version of CLaMS that calculates the growth and sedimentation of nitric acid trihydrate (NAT) particles along individual particle trajectories. From those, we derive the HNO₃ downward flux resulting from different particle nucleation assumptions. The simulation results show a clear vertical redistribution of total inorganic nitrogen ( ), with a maximum vortex average permanent removal of over 5ppb in late December between 500 and 550K and a corresponding increase of of over 2ppb below about 450K. The simulated vertical redistribution of is compared with balloon observations by MkIV and in-situ observations from the high altitude aircraft Geophysica. Assuming a globally uniform NAT particle nucleation rate of 7.8x10^-6cm^-3h^-1 in the model, the observed denitrification is well reproduced. <P style="line-height: 20px;"> In the investigated winter 2002/2003, the denitrification has only moderate impact (&le;14%) on the simulated vortex average ozone loss of about 1.1ppm near the 460K level. At higher altitudes, above 600K potential temperature, the simulations show significant ozone depletion through -catalytic cycles due to the unusual early exposure of vortex air to sunlight.

• GPS radio occultation with CHAMP and SAC-C: global monitoring of thermal tropopause parameters

  In this study the global lapse-rate tropopause (LRT) pressure, temperature, potential temperature, and sharpness are discussed based on Global Positioning System (GPS) radio occultations (RO) from the German CHAMP (CHAllenging Minisatellite Payload) and the U.S.-Argentinian SAC-C (Satelite de Aplicaciones Cientificas-C) satellite missions. Results with respect to seasonal variations are compared with operational radiosonde data and ECMWF (European Centre for Medium-Range Weather Forecast) operational analyses. Results on the tropical quasi-biennial oscillation (QBO) are updated from an earlier study. CHAMP RO data are available continuously since May 2001 with on average 150&nbsp;high resolution temperature profiles per day. SAC-C data are available for several periods in 2001 and 2002. In this study temperature data from CHAMP for the period May 2001-December 2004 and SAC-C data from August 2001-October 2001 and March 2002-November 2002 were used, respectively. The bias between GPS RO temperature profiles and radiosonde data was found to be less than 1.5K between 300 and 10hPa with a standard deviation of 2-3K. Between 200-20hPa the bias is even less than 0.5K (2K standard deviation). The mean deviations based on 167699&nbsp;comparisons between CHAMP/SAC-C and ECMWF LRT parameters are (-2.1&plusmn;37.1)hPa for pressure and (0.1&plusmn;4.2)K for temperature. Comparisons of LRT pressure and temperature between CHAMP and nearby radiosondes (13230) resulted in (5.8&plusmn;19.8)hPa and (-0.1&plusmn;3.3)K, respectively. The comparisons between CHAMP/SAC-C and ECMWF show on average the largest differences in the vicinity of the jet streams with up to 700m in LRT altitude and 3K in LRT temperature, respectively. The CHAMP mission generates the first long-term RO data set. Other satellite missions will follow (GRACE, COSMIC, MetOp, TerraSAR-X, EQUARS) generating together some thousand temperature profiles daily.

• Systematic errors in global air-sea CO2 flux caused by temporal averaging of sea-level pressure

  Long-term temporal averaging of meteorological data, such as wind speed and air pressure, can cause large errors in air-sea carbon flux estimates. Other researchers have already shown that time averaging of wind speed data creates large errors in flux due to the non-linear dependence of the gas transfer velocity on wind speed (Bates and Merlivat, 2001). However, in general, wind speed is negatively correlated with air pressure, and a given fractional change in the pressure of dry air produces an equivalent fractional change in the atmospheric partial pressure of carbon dioxide (pCO_2air). Thus low pressure systems cause a drop in pCO_2air, which together with the associated high winds, promotes outgassing/reduces uptake of CO₂ from the ocean. Here we quantify the errors in global carbon flux estimates caused by using monthly or climatological pressure data to calculate pCO_2air (and thus ignoring the covariance of wind and pressure) over the period 1990-1999, using two common parameterisations for gas transfer velocity. Results show that on average, compared with estimates made using 6 hourly pressure data, the global oceanic sink is systematically overestimated by 7% (W92) and 10% (WM99) when monthly mean pressure is used, and 9% (W92) and 12% (WM99) when climatological pressure is used.

• One-year record of organic and elemental carbon in fine particles in downtown Beijing and Shanghai

  Weekly PM_2.5 samples were collected for one year (1999-2000) in Beijing and Shanghai and the carbonaceous species analyzed to investigate and compare their time series patterns and possible sources in the two biggest cities of China. Weekly carbonaceous concentrations varied in wide ranges with 8.6-59&micro;g m^-3 for OC and 1.5-25.4&micro;g m^-3 for EC in Beijing, and with 5.1-38.4&micro;g m^-3 for OC and 2.3-13.0&micro;g m^-3 for EC in Shanghai. Similar weekly and seasonal variations of OC and EC concentrations were found in each city though major combustion sources presented source-dependent emission characteristics and seasonal differences in emission amount for carbonaceous species. Both OC and EC maintained much higher concentrations in late fall through winter, probably due to enhanced emissions coupled with unfavorable meteorological conditions. In Beijing, the ¹⁴C analysis of limited samples suggested there was a significant contribution (33-48%) of modern carbon to the total fine carbonaceous PM burden with higher fractions in the harvest seasons. The high mass ratios of excessive potassium to EC in both Beijing and Shanghai also indicated that biomass burning had important contribution to fine carbonaceous particles.

• Evidence for long-lived polar vortex air in the mid-latitude summer stratosphere from in situ laser diode CH4 and H2O measurements

  A balloon borne diode laser spectrometer was launched in southern France in June 2000 to yield in situ stratospheric CH₄ and H₂O measurements. In the altitude region ranging from 20km to 25km, striking large spatial structures were observed in the vertical concentration profiles of both species. We suggest these patterns are due to the presence of long-lived remnants of the wintertime polar vortex in the mid-latitude summer stratosphere. To support this interpretation, a high resolution advection model for potential vorticity is used to investigate the evolution of the Arctic vortex after its breakdown phase in spring 2000.

• Nanoparticle formation by ozonolysis of inducible plant volatiles

  We present the first laboratory experiments of aerosol formation from oxidation of volatile organic species emitted by living plants, a process which for half a century has been known to take place in the atmosphere. We have treated white cabbage plants with methyl jasmonate in order to induce the production of monoterpenes and certain less-volatile sesqui- and homoterpenes. Ozone was introduced into the growth chamber in which the plants were placed, and the subsequent aerosol formation and growth of aerosols were monitored by measuring the particle size distributions continuously during the experiments. Our observations show similar particle formation rates as in the atmosphere but much higher growth rates. The results indicate that the concentrations of nonvolatile oxidation products of plant released precursors needed to induce the nucleation are roughly an order-of-magnitude higher than their concentrations during atmospheric nucleation events. Our results therefore suggest that if oxidized organics are involved in atmospheric nucleation events, their role is to participate in the growth of pre-existing molecular clusters rather than to form such clusters through homogeneous or ion-induced nucleation.

• Water activity in polyol/water systems: new UNIFAC parameterization

  Water activities of a series of polyol/water systems were measured with an AquaLab dew point water activity meter at 298K. The investigated polyols with carbon numbers from <i>n</i>=2-7 are all in liquid state at room temperature and miscible at any molar ratio with water. In aqueous solutions with the same molar concentration, the diols with lower molecular weight lead to lower water activities than those with higher molecular weights. For diols with four or more carbon atoms, the hydrophilicity shows considerable differences between isomers: The 1,2-isomers - consisting of a hydrophilic and a hydrophobic part - bind less strongly to water than isomers with a more balanced distribution of the hydroxyl groups. The experimental water activities were compared with the predictions of the group contribution method UNIFAC: the model predictions overestimate the water activity of water/polyol systems of substances with two or more hydroxyl groups and can not describe the decreased binding to water of isomers with hydrophobic tails. To account for the differences between isomers, a modified UNIFAC parameterization was developed, that allows to discriminate between three types of alkyl groups depending on their position in the molecule. These new group interaction parameters were calculated using water activities of alcohol/water mixtures. This leads to a distinctly improved agreement of model predictions with experimental results while largely keeping the simplicity of the functional group approach.

• Spatial and temporal distribution of atmospheric aerosols in the lowermost troposphere over the Amazonian tropical rainforest

  We present measurements of aerosol physico-chemical properties below 5 km altitude over the tropical rain forest and the marine boundary layer (MBL) obtained during the LBA-CLAIRE 1998 project. The MBL aerosol size distribution some 50-100km of the coast of French Guyana and Suriname showed a bi-modal shape typical of aged and cloud processed aerosol. The average particle number density in the MBL was 383cm^-3. The daytime mixed layer height over the rain forest for undisturbed conditions was estimated to be between 1200-1500m. During the morning hours the height of the mixed layer increased by 144-180mh^-1. The median daytime aerosol number density in the mixed layer increased from 450cm^-3 in the morning to almost 800cm^-3 in the late afternoon. The evolution of the aerosol size distribution in the daytime mixed layer over the rain forest showed two distinct patterns. Between dawn and midday, the Aitken mode particle concentrations increased, whereas later during the day, a sharp increase of the accumulation mode aerosol number densities was observed, resulting in a doubling of the morning accumulation mode concentrations from 150cm^-3 to 300cm^-3. Potential sources of the Aitken mode particles are discussed here including the rapid growth of ultrafine aerosol particles formed aloft and subsequently entrained into the mixed layer, as well as the contribution of emissions from the tropical vegetation to Aitken mode number densities. The observed increase of the accumulation mode aerosol number densities is attributed to the combined effect of: the direct emissions of primary biogenic particles from the rain forest and aerosol in-cloud processing by shallow convective clouds. Based on the similarities among the number densities, the size distributions and the composition of the aerosol in the MBL and the nocturnal residual layer we propose that the air originating in the MBL is transported above the nocturnal mixed layer up to 300-400km inland over the rain forest by night without significant processing.

• Initial validation of ENVISAT/SCIAMACHY columnar CO by FTIR profile retrievals at the Ground-Truthing Station Zugspitze

  Carbon monoxide vertical profile retrievals from ground-based solar FTIR measurements at the Permanent Ground-Truthing Station Zugspitze (47.42&deg; N, 10.98&deg; E, 2964m a.s.l.), Germany are used to validate columnar CO retrieved from ENVISAT/SCIAMACHY spectra (WFM-DOAS version 0.4). The WFM-DOAS retrievals of CO include an empirical column scaling factor of 0.5. Therefore, not absolute column levels are validated, but the proper response of the SCIAMACHY retrievals to the atmospheric inter-annual variability is quantitatively assessed in comparison to the Zugspitze FTIR results. Although CO WFM-DOAS data for only 33 days were available for this study (data covering January-October 2003), it is possible to retrieve information on the CO annual cycle (&asymp;10% amplitude) in a statistically significant fit out of the scatter of the SCIAMACHY WFM-DOAS data. To obtain this, all pixels within a minimum radius of 2000km around Zugspitze had to be averaged for each day.

• Parametric sensitivity and uncertainty analysis of dimethylsulfide oxidation in the clear-sky remote marine boundary layer

  Local and global sensitivity and uncertainty methods are applied to a box model of the dimethylsulfide (DMS) oxidation cycle in the remote marine boundary layer in order to determine the key physical and chemical parameters and sources of uncertainty. The model considers 58&nbsp;uncertain parameters, and simulates the diurnal gas-phase cycles of DMS, SO₂, methanesulfonic acid (MSA), and H₂SO₄ for clear-sky summertime conditions observed over the Southern Ocean. The results of this study depend on many underlying assumptions, including the DMS mechanism, simulation conditions, and probability distribution functions of the uncertain parameters. A local direct integration method is used to calculate first-order local sensitivity coefficients for infinitesimal perturbations about the parameter means. Key parameters identified by this analysis are related to DMS emissions, vertical mixing, heterogeneous removal, and the DMS+OH abstraction and addition reactions. MSA and H₂SO₄ are also sensitive to numerous rate constants, which limits the ability of using parameterized mechanisms to predict their concentrations. Of the chemistry, H₂SO₄ is highly sensitive to the rate constants for a set of nighttime reactions that lead to its production through a non-SO₂ path initiated by the oxidation of DMS by NO₃. For the global analysis, the probabilistic collocation method is used to propagate the uncertain parameters through the model. The concentrations of DMS and SO₂ are uncertain (1-&sigma;) by factors of 3.5 and 2.5, respectively, while MSA and H₂SO₄ have uncertainty factors that range between 4.1 and 8.6. The main sources of uncertainty in the four species are from DMS emissions and heterogeneous scavenging, but the uncertain rate constants collectively account for up to 59% of the total uncertainty in MSA and 43% in H₂SO₄. Of the uncertain DMS chemistry, reactions that form and destroy CH₃S(O)OO and CH₃SO₃ are identified as important targets for reducing the uncertainties.