ALBERT

Description: A strong pollution episode in the upper troposphere between South China and the Philippines was observed during CARIBIC flights in April 2007. Five pollution events were observed, where enhancements in aerosol and trace gas concentrations including CO, CO2, CH4, non-methane hydrocarbons (NMHCs) and halocarbons were observed along the flight tracks during four sequential flights. The importance of the contribution of biomass/biofuel burning was investigated using chemical tracers, emission factor analysis, back-trajectory analysis and satellite images. The Indochinese peninsula was identified as the probable source region of biomass/biofuel burning. However, enhancements in the urban/industrial tracer C2Cl4 during the events also indicate a substantial contribution from urban anthropogenic emissions. An estimation of the contribution of fossil fuel versus biomass/biofuel to the CO enhancement was made, indicating a biomass/biofuel burning contribution of ~54 to ~92% of the observed CO enhancements. Biomass/biofuel burning was found to be the most important source category during the sampling period.

Description: Airborne lidar and in-situ measurements of aerosols and trace gases were performed in volcanic ash plumes over Europe between Southern Germany and Iceland with the Falcon aircraft during the eruption period of the Eyjafjalla volcano between 19 April and 18 May 2010. Flight planning and measurement analyses were supported by a refined Meteosat ash product and trajectory model analysis. The volcanic ash plume was observed with lidar directly over the volcano and up to a distance of 2700 km downwind, and up to 120 h plume ages. Aged ash layers were between a few 100 m to 3 km deep, occurred between 1 and 7 km altitude, and were typically 100 to 300 km wide. Particles collected by impactors had diameters up to 20 μm diameter, with size and age dependent composition. Ash mass concentrations were derived from optical particle spectrometers for a particle density of 2.6 g cm−3 and various values of the refractive index (RI, real part: 1.59; 3 values for the imaginary part: 0, 0.004 and 0.008). The mass concentrations, effective diameters and related optical properties were compared with ground-based lidar observations. Theoretical considerations of particle sedimentation constrain the particle diameters to those obtained for the lower RI values. The ash mass concentration results have an uncertainty of a factor of two. The maximum ash mass concentration encountered during the 17 flights with 34 ash plume penetrations was below 1 mg m−3. The Falcon flew in ash clouds up to about 0.8 mg m−3 for a few minutes and in an ash cloud with approximately 0.2 mg m−3 mean-concentration for about one hour without engine damage. The ash plumes were rather dry and correlated with considerable CO and SO2 increases and O3 decreases. To first order, ash concentration and SO2 mixing ratio in the plumes decreased by a factor of two within less than a day. In fresh plumes, the SO2 and CO concentration increases were correlated with the ash mass concentration. The ash plumes were often visible slantwise as faint dark layers, even for concentrations below 0.1 mg m−3. The large abundance of volatile Aitken mode particles suggests previous nucleation of sulfuric acid droplets. The effective diameters range between 0.2 and 3 μm with considerable surface and volume contributions from the Aitken and coarse mode aerosol, respectively. The distal ash mass flux on 2 May was of the order of 500 (240–1600) kg s−1. The volcano induced about 10 (2.5–50) Tg of distal ash mass and about 3 (0.6–23) Tg of SO2 during the whole eruption period. The results of the Falcon flights were used to support the responsible agencies in their decisions concerning air traffic in the presence of volcanic ash.

Description: The CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flying laboratory measures once per month the chemical composition at cruise altitude (10...12 km) during 4 consecutive Lufthansa flights. Here we present a case study of enhanced nitrogen oxides (NOx), nitrous acid (HONO), and formaldehyde (HCHO) in a thunderstorm cloud over the Caribbean islands of Guadeloupe in August 2011. Nitrous acid is an important reservoir gas for OH radicals, and only few observations of HONO at cruise altitude exist. CARIBIC is designed as a long period atmospheric observation system, the actual system has been flying almost monthly since 8 yr now. During this period only very few similar events (one since 2008) were observed. Due to multiple scattering the light path inside clouds is enhanced, thereby lowering the detection limit of the DOAS instrument. Under background conditions the detection limits are 46 ppt for HONO, 387 ppt for chem{HCHO}, and 100 ppt for NO2 and are roughly three times lower inside the cloud. Based on radiative transfer simulations we estimate the path length to 90{ldots}100 km and the cloud top height to ≈15 km. The inferred mixing ratios of HONO, HCHO and NO2 are 37 ppt, 400 ppt and 170 ppt, respectively. Bromine monoxide (BrO) remained below the detection limit of 1 ppt. Because the uplifted air masses originated from the remote marine boundary layer and lightning was observed in the area by the World Wide Lightning Location Network several hours prior to the measurement, the NO (≈1.5 ppb) enhancement was in all likelihood caused by lightning. The main source for the observed HCHO is probably updraught from the boundary layer, because the chemical formation of formaldehyde due to methane oxidation is too weak. Besides HCHO also CH3OOH and isoprene are considered as precursors. The chemical box model CAABA is used to estimate the chem{NO} and HCHO source strengths, which are necessary to explain our measurements. For NO a source strength of 8.25 × 109 molec cm−2 s−1 km−1 is found, which corresponds to the lightning activity as observed by the World Wide Lightning Location network and a lightning emission of 4.2 × 1025 NO molec/flash. The HCHO updraught is of the order of 121 × 109 molec cm−2 s−1 km−1. Also isoprene and CH3OOH as possible HCHO sources were studied and similar source strengths were found.

Description: The formation, abundance and distribution of organic nitrates are relevant for determining the production efficiency and resident mixing ratios of tropospheric ozone (O3) at both regional and global scales. Here we investigate the effect of applying the recently measured direct chemical production of methyl nitrate (CH3ONO2) during NOx recycling involving the methyl-peroxy radical on the global tropospheric distribution of CH3ONO2 and the perturbations introduced towards tropospheric NOx and O3 using the TM5 global chemistry transport model. By comparing against numerous observations we show that the global surface distribution of CH3ONO2 can be largely explained by introducing the chemical production mechanism using a branching ratio of 0.3%, when assuming a direct oceanic emission source of ~0.29 Tg N yr−1. The resident mixing ratios are found to be highly sensitive towards the dry deposition velocity of CH3ONO2 that is prescribed, where more than 50% of the direct oceanic emission of CH3ONO2 is lost near the source regions thereby mitigating subsequent effects on tropospheric composition due to long range and convective transport. For the higher alkyl nitrates (C2 and above) we find improvements in their simulated distribution in the tropics in TM5 improves when introducing direct oceanic emissions of ~0.17 Tg N yr−1. For the tropical upper troposphere (UT) a significant low model bias for all alkly nitrates occurs due to either missing transport pathways or chemical precursors, although measurements show significant variability in resident mixing ratios at high altitudes with respect to both latitude and longitude. For total reactive nitrogen (NOy) ~20% originates from alkyl nitrates in the tropical and extra-tropical UT, where the introduction of both direct oceanic emission sources and the chemical production of CH3ONO2 only increases NOy by ~5% when compared with aircraft observations. We find that the increases in tropospheric O3 due to direct oceanic emissions are mitigated by introducing the direct chemical production of CH3ONO2 resulting in rather moderate effects on nitrogen oxides and tropospheric O3.

Description: Airborne measurements of Lidar backscatter, aerosol concentrations (particle diameters of 4 nm to 50 μm), trace gas mixing ratios (SO2, CO, O3, H2O), single particle properties, and meteorological parameters have been performed in volcanic ash plumes with the Falcon aircraft operated by Deutsches Zentrum für Luft- und Raumfahrt (DLR). A series of 17 flights was performed over Europe between Southern Germany and Iceland during the eruption period of the Eyjafjalla1 volcano between 19 April and 18 May 2010. Flight planning and measurement analyses were supported by a refined Meteosat ash product and trajectory model analysis. The volcanic ash plume was observed with Lidar directly over the volcano and up to a distance of 2700 km downwind. Lidar and in-situ measurements covered plume ages of 7 h to 120 h. Aged ash layers were between a few 100 m to 3 km deep, occurred between 1 and 7 km altitude, and were typically 100 to 300 km wide. Particles collected by impactors had diameters up to 20 μm diameter, with size and age dependent composition. Ash mass concentration was evaluated for a material density of 2.6 g cm−3 and for either weakly or moderately absorbing coarse mode particles (refractive index 1.59+0i or 1.59+0.004i). In the absorbing case, the ash concentration is about a factor of four larger than in the non-absorbing limit. Because of sedimentation constraints, the smaller results are the more realistic ones for aged plumes. The Falcon flew in ash clouds up to about 1 mg m−3 for a few minutes and in an ash cloud with more than 0.2 mg m−3 mean-concentration for about one hour without engine damages. In fresh plumes, the SO2 concentration was correlated with the ash mass concentration. Typically, 0.5 mg m−3 ash concentration was related to about 100 nmol mol−31 SO2 mixing ratio and 70 nmol mol−1 CO mixing ratio increases for this volcano period. In aged plumes, layers with enhanced coarse mode particle concentration but without SO2 enhancements occurred. To first order, ash concentration and SO2 mixing ratio in the plumes decreased by a factor of two within less than a day. The ash plumes were often visible as faint dark layers even for concentrations below 0.1 mg m−3. The ozone concentrations and the humidity inside the plumes were often reduced compared to ambient values. The large abundance of volatile Aitken mode particles suggests nucleation of sulfuric acid droplets. Ammonium sulfate particles were also found on the impactors. The effective diameters decreased from about 5 μm in the fresh plume to about 1 μm for plume ages of up to 6 days. The distal ash mass flux on 2 May was of the order 1800 kg s−1; the SO2 mass flux was about a factor of 3–4 smaller. The volcano ejected about 40 Tg of ash mass and 10 Tg of SO2 during the whole eruption period. The results of the Falcon flights were used to support the responsible agencies in their decisions concerning air traffic in the presence of volcanic ash. The data described may be used for further studies, including comparisons to satellite and ground or space based Lidar observations, and for model improvements. 1 Also known as Eyjafjallajökull or Eyjafjöll volcano, http://www.britannica.com/EBchecked/topic/1683937/Eyjafjallajokull-volcano

Description: The chemistry in large thunderstorm clouds is influenced by local lightning-NOx production and uplift of boundary layer air. Under these circumstances trace gases like nitrous acid (HONO) or formaldehyde (HCHO) are expected to be formed or to reach the tropopause region. However, up to now only few observations of HONO at this altitude have been reported. Here we report on a case study where enhancements in HONO, HCHO and nitrogen oxides (NOx) were observed by the CARIBIC flying laboratory (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container). The event took place in a convective system over the Caribbean Sea in August 2011. Inside the cloud the light path reaches up to 100 km. Therefore the DOAS instrument on CARIBIC was very sensitive to the tracers inside the cloud. Based on the enhanced slant column densities of HONO, HCHO and NO2, average mixing ratios of 37, 468 and 210 ppt, respectively, were calculated. These data represent averages for constant mixing ratios inside the cloud. However, a large dependency on the assumed profile is found; for HONO a mixing ratio of 160 ppt is retrieved if the total amount is assumed to be situated in the uppermost 2 km of the cloud. The NO in situ instrument measured peaks up to 5 ppb NO inside the cloud; the background in the cloud was about 1.3 ppb, and hence clearly above the average outside the cloud (≈ 150 ppt). The high variability and the fact that the enhancements were observed over a pristine marine area led to the conclusion that, in all likelihood, the high NO concentrations were caused by lighting. This assumption is supported by the number of flashes that the World Wide Lightning Location Network (WWLLN) counted in this area before and during the overpass. The chemical box model CAABA is used to estimate the NO and HCHO source strengths which are necessary to explain our measurements. For NO a source strength of 10 × 109 molec cm−2 s−1 km−1 is found, which corresponds to the lightning activity as observed by the World Wide Lightning Location network, and lightning emissions of 5 × 1025 NO molec flash−1 (2.3–6.4 × 1025). The uncertainties are determined by a change of the input parameters in the box model, the cloud top height and the flash density. The emission rate per flash is scaled up to a global scale and 1.9 (1.4–2.5) tg N a−1 is estimated. The HCHO updraught is of the order of 120 × 109 molec cm−2 s−1 km−1. Also isoprene and CH3OOH as possible HCHO sources are discussed.

Description: The formation, abundance and distribution of organic nitrates are relevant for determining the production efficiency and resident mixing ratios of tropospheric ozone (O3) on both regional and global scales. Here we investigate the effect of applying the recently measured direct chemical production of methyl nitrate (CH3ONO2) during NOx recycling involving the methyl-peroxy radical on the global tropospheric distribution of CH3ONO2 and the perturbations introduced towards tropospheric NOx and O3 using the TM5 global chemistry transport model. By comparisons against numerous observations, we show that the global surface distribution of CH3ONO2 can be largely explained by introducing the chemical production mechanism using a branching ratio of 0.3%, when assuming a direct oceanic emission source of ~0.15 Tg N yr−1. On a global scale, the chemical production of CH3ONO2 converts 1 Tg N yr−1 from nitrogen oxide for this branching ratio. The resident mixing ratios of CH3ONO2 are found to be highly sensitive to the dry deposition velocity that is prescribed, where more than 50% of the direct oceanic emission is lost near the source regions, thereby mitigating the subsequent effects due to long-range and convective transport out of the source region. For the higher alkyl nitrates (RONO2) we find improvements in the simulated distribution near the surface in the tropics (10° S–10° N) when introducing direct oceanic emissions equal to ~0.17 Tg N yr−1 . In terms of the vertical profile of CH3ONO2, there are persistent overestimations in the free troposphere and underestimations in the upper troposphere across a wide range of latitudes and longitudes when compared against data from measurement campaigns. This suggests either a missing transport pathway or source/sink term, although measurements show significant variability in resident mixing ratios at high altitudes at global scale. For the vertical profile of RONO2, TM5 performs better at tropical latitudes than at mid-latitudes, with similar features in the comparisons to those for CH3ONO2. Comparisons of CH3ONO2 with a wide range of surface measurements shows that further constraints are necessary regarding the variability in the deposition terms for different land surfaces in order to improve on the comparisons presented here. For total reactive nitrogen (NOy) ~20% originates from alkyl nitrates in the tropics and subtropics, where the introduction of both direct oceanic emissions and the chemical formation mechanism of CH3ONO2 only makes a ~5% contribution to the total alkyl nitrate content in the upper troposphere when compared with aircraft observations. We find that the increases in tropospheric O3 that occur due oxidation of CH3ONO2 originating from direct oceanic emission is negated when accounting for the chemical formation of CH3ONO2, meaning that the impact of such oceanic emissions on atmospheric lifetimes becomes marginal when a branching ratio of 0.3% is adopted.