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Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations

We construct a global atmospheric budget for acetaldehyde using a 3-D model of atmospheric chemistry (GEOS-Chem), and use an ensemble of observations to evaluate present understanding of its sources and sinks. Hydrocarbon oxidation provides the largest acetaldehyde source in the model (128 Tg a−1, a factor of 4 greater than the previous estimate), with alkanes, alkenes, and ethanol the main precursors. There is also a minor source from isoprene oxidation. We use an updated chemical mechanism for GEOS-Chem, and photochemical acetaldehyde yields are consistent with the Master Chemical Mechanism. We present a new approach to quantifying the acetaldehyde air-sea flux based on the global distribution of light absorption due to colored dissolved organic matter (CDOM) derived from satellite ocean color observations. The resulting net ocean emission is 57 Tg a−1, the second largest global source of acetaldehyde. A key uncertainty is the acetaldehyde turnover time in the ocean mixed layer, with quantitative model evaluation over the ocean complicated by known measurement artifacts in clean air. Simulated concentrations in surface air over the ocean generally agree well with aircraft measurements, though the model tends to overestimate the vertical gradient. PAN:NOx ratios are well-simulated in the marine boundary layer, providing some support for the modeled ocean source. We introduce the Model of Emissions of Gases and Aerosols from Nature (MEGANv2.1) for acetaldehyde and ethanol and use it to quantify their net flux from living terrestrial plants. Including emissions from decaying plants the total direct acetaldehyde source from the land biosphere is 23 Tg a−1. Other terrestrial acetaldehyde sources include biomass burning (3 Tg a−1) and anthropogenic emissions (2 Tg a−1). Simulated concentrations in the continental boundary layer are generally unbiased and capture the spatial gradients seen in observations over North America, Europe, and tropical South America. However, the model underestimates acetaldehyde levels in urban outflow, suggesting a missing source in polluted air. Ubiquitous high measured concentrations in the free troposphere are not captured by the model, and based on present understanding are not consistent with concurrent measurements of PAN and NOx: we find no compelling evidence for a widespread missing acetaldehyde source in the free troposphere. We estimate the current US source of ethanol and acetaldehyde (primary + secondary) at 1.3 Tg a−1 and 7.8 Tg a−1, approximately 60{%} and 480% of the corresponding increases expected for a national transition from gasoline to ethanol fuel.
Study on the impact of sudden stratosphere warming in the upper mesosphere-lower thermosphere regions using satellite and HF radar measurements

The occurrence of a sudden stratospheric warming (SSW) excites disturbances in the mesosphere-lower thermospheric (MLT) wind and temperature. Here, we have examined the high frequency (HF) radar wind data from the South African National Antarctic Expedition, SANAE (72° S, 3° W), a radar which is part of the Super Dual Auroral Radar Network (SuperDARN). Sounding of the Atmosphere using Broadband Emission Radiometry (SABER) on board the Thermosphere-Ionosphere-Mesosphere-Energetics and Dynamics (TIMED) satellite temperature data and National Centre for Environmental Prediction (NCEP) temperature and wind data are used to investigate the dynamical effects of the unprecedented September 2002 SSW in the Antarctica stratosphere and MLT. The mean zonal wind (from SANAE HF radar) at the MLT shows reversal approximately 7 days before the reversal at 10 hPa (from NCEP). This indicates that there was a downwards propagation of circulation disturbance. Westerly zonal winds dominate the winter MLT, but during the 2002 winter there are many periods of westward winds observed compared to other years. The normalised power spectrums of both meridional and zonal winds show presence of planetary waves (of ~14-day period) before the occurrence of the SSW. The SABER vertical temperature profiles indicated the cooling of the MLT region before the SSW event.
Sensitivity of tracer transport to model resolution, prescribed meteorology and tracer lifetime in the general circulation model ECHAM5

Atmospheric transport of traces gases and aerosols plays an important role in the distribution of air pollutants and radiatively active compounds. For model simulations of chemistry-climate interactions it is important to know how the transport of tracers depends on the geographical resolution of the general circulation model. However, this aspect has been scarcely investigated until now. Here, we analyse tracer transport in the ECHAM5 general circulation model using 6 independent idealized tracers with constant lifetimes, which are released in two different altitudes at the surface and in the stratosphere, respectively. Model resolutions from T21L19 to T106L31 were tested by performing multi-annual simulations with prescribed sea surface temperatures and sea ice fields of the 1990s. The impacts of the tracer lifetime were investigated by varying the globally uniform exponential decay time between 0.5 and 50 months. We also tested the influence of using prescribed meteorological fields (ERA40) instead of climatological sea surface temperature and sea ice fields. Meridional transport of surface tracers decreases in the coarse resolution model due to enhanced vertical mixing, with the exception of the advection into the tropical region, which shows an inconsistent trend between the resolutions. Whereas, the meridional transport of tracers released in the stratosphere was enhanced with higher model resolutions, except in the transport from tropical stratosphere to the Southern Hemisphere, which exhibits an increase trend with increasing model resolution. The idealized tracers exhibit a seasonal cycle, which is modulated by the tracer lifetime. In comparison to the run with prescribed sea surface temperature and sea ice fields, the simulation with prescribed meteorological fields did not exhibit significant change in the meridional transport, except in the exchange of stratospheric tracers between both hemispheres, where it causes about 100% increase. The import of the surface tracers into the stratosphere is increased by up to a factor of 2.5, and the export from the stratosphere into the troposphere was increased by up to 60% when prescribed meteorological fields is used. The ERA40 simulation also showed larger interannual variability (up to 24% compared to 12% in the standard simulations). Using our surface tracers released in either the northern or Southern Hemisphere, respectively, we calculate inter-hemispheric transport times between 11 and 17 months, consistent with values reported in the literature. While this study cannot be used to relate differences in model results to specific changes in transport processes, it nevertheless provides some insight into the characteristics of tracer transport in the widely used ECHAM5 general circulation model.
Composition and sources of particulate matter in an industrialised Alpine valley

A three-week long field campaign was carried out under autumnal meteorological conditions at four valley floor sites in the industrialised Swiss Rhone Valley. For one week of stable meteorological conditions, particulate matter with an aerodynamic diameter below 10 μm (PM10) was analysed from daily filters using ion chromatography, X-ray fluorescence, anhydrosugars and radiocarbon analysis of the organic and elemental matter (OM and EM, respectively). Furthermore, PM1 composition along the whole campaign was monitored in Massongex (a site near industries) by a seven-wavelength aethalometer and a quadrupole aerosol mass spectrometer (Q-AMS). At all sites, PM10 secondary inorganics and non-fossil EM and OM exhibited relatively stable concentrations over the selected days. On the contrary, PM10 fossil carbonaceous fractions, mineral dust components and several trace elements showed a significant decrease on Sunday, compared to the analysed working days. Their concentrations were also highly correlated. This evidenced the role of exhaust and resuspension emissions by heavy-duty vehicle traffic to the PM10 concentrations along the valley. In Massongex, organic matter and black carbon (BC) were the main contributors to PM1 over the campaign (accounting for 45% and 18% of PM1, respectively). An optical discrimination of BC highlighted the prevalence of fossil over wood-burning sources. Three types of PM1 organics could be identified by factor analysis: primary wood-burning organic aerosol (P-WBOA) dominated the PM1 carbonaceous fraction, followed by oxygenated organics (OOA) mostly representing secondary organics, and by traffic or possibly industry-related hydrocarbon-like organics (HOA) as the smallest carbonaceous contribution. Furthermore, unusually high contributions of fine chloride were detected at all sites. They were attributed to ammonium chloride (NH4Cl) in Massongex and represented the only significant component exclusively attributable to industrial emissions.
Pressure dependence of the deuterium isotope effect in the photolysis of formaldehyde by ultraviolet light

The pressure dependence of the relative photolysis rate of HCHO vs. HCDO has been investigated for the first time, using a photochemical reactor at the University of Copenhagen. The dissociation of HCHO vs. HCDO using a UVA lamp was measured at total bath gas pressures of 50, 200, 400, 600 and 1030 mbar. The products of formaldehyde photodissociation are either H2 + CO (molecular channel) or HCO + H (radical channel), and a photolysis lamp was chosen to emit light at wavelengths that greatly favor the molecular channel. The isotope effect in the dissociation, kHCHO/kHCDO, was found to depend strongly on pressure, varying from 1.1 + 0.15/−0.1 at 50 mbar to 1.75±0.10 at 1030 mbar. The results can be corrected for radical channel contribution to yield the kinetic isotope effect for the molecular channel; i.e. the KIE in the production of molecular hydrogen. This is done and the results at 1030 mbar are discussed in relation to previous studies at ambient pressure. In the atmosphere the relative importance of the two product channels changes with altitude as a result of changes in pressure and actinic flux. The study demonstrates that the δD of photochemical hydrogen produced from formaldehyde will increase substantially as pressure decreases.
Sediment records of highly variable mercury inputs to mountain lakes in Patagonia during the past millennium

High Hg levels in the pristine lacustrine ecosystems of the Nahuel Huapi National Park, a protected zone situated in the Andes of Northern Patagonia, Argentina, have initiated further investigations on Hg cycling and source identification. Here we report Hg records in sedimentary sequences to identify atmospheric sources during the past millennium. In addition to global transport and deposition, a potential atmospheric Hg source to be considered is the local emissions associated with volcanic activity, because the Park is situated in the Southern Volcanic Zone. Two sediment cores were extracted from Lake Tonček, a small, high-altitude system reflecting mainly direct inputs associated with atmospheric contributions, and Lake Moreno Oeste, a much larger and deeper lake having an extended watershed covered mostly by native forest. The sedimentary sequences were dated based on both 210Pb and 137Cs profiles. In addition, tephra layers were identified and geochemically characterized for chronological application and to investigate any association of volcanic eruptions with Hg records. Hg concentrations in sediments were measured along with 32 other elements, as well as organic matter, subfossil chironomids, and biogenic silica. Observed background Hg concentrations, determined from the sequence domains with lower values, ranged from 50 to 100 ng g−1 dry weight (DW), whereas the surficial layers reached 200 to 500 ng g−1 DW. In addition to this traditional pattern, however, two deep domains in both sequences showed dramatically increased Hg levels reaching 400 to 650 ng g−1 DW; the upper dated to the 18th to 19th centuries, and the lower around the 13th century. These concentrations are not only elevated in the present profiles but also many-fold above the background values determined in other fresh water sediments, as were also the Hg fluxes, reaching 120 to 150 μg m−2 y−1 in Lake Tonček . No correlation was observed between Hg concentrations and the contents of organic matter, subfossil chironomids, biogenic silica, or the other elements determined. However, distinctly increased Hg concentrations were observed immediately above some tephra layers, suggesting a link to volcanic events. Extended fires might be another potential atmospheric source because the earlier Hg peaks coincide with reported charcoal peaks, whereas the upper Hg peaks coincide with evidences of extended forest fires from tree-ring data and historical records.
Amine exchange into ammonium bisulfate and ammonium nitrate nuclei

The exchange kinetics and thermodynamics of amines for ammonia in small (1–2 nm diameter) ammonium bisulfate and ammonium nitrate clusters were investigated using electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS). Ammonium salt clusters were reacted with amine gas at constant pressure to determine the kinetics of exchange. The reverse reactions, where aminium salt clusters reacted with ammonia gas, were also studied, and no substitution of ammonia for amine was observed. Gibbs free energy changes for these substitutions were determined to be highly exothermic, −7 kJ/mol or more negative in all cases. Uptake coefficients (reaction probabilities) were found to be near unity, implying that complete exchange of ammonia in small clusters by amine would be expected to occur within several seconds to minutes in the ambient atmosphere. These results suggest that if salt clusters are a component of the sub-3 nm cluster pool, they are likely to be aminium salts rather than ammonium salts, even if they were initially formed as ammonium salts.
Numerical simulation of tropospheric injection of biomass burning products by pyro-thermal plumes

The thermal plume model, a mass-flux scheme originally developed to represent the vertical transport by convective structures within the boundary layer, is adapted to the representation of plumes generated by fires, with the aim of estimating the height at which fire emissions are actually injected in the atmosphere. The parameterization, which takes into account the excess of near surface temperature induced by fires and the mixing between convective plumes and environmental air, is first evaluated on two well-documented fires. Simulations over Southern Africa performed with the general circulation model LMDZ over one month show that the CO2 can be injected far above the boundary layer height, leading to a daily excess of CO2 in the mid-troposphere of an order of 2 ppmv. These results agree with satellite retrievals of a diurnal cycle of CO2 in the free troposphere over regions affected by biomass burning in the Tropics.
Do biomass burning aerosols intensify drought in equatorial Asia during El Niño?

During El Niño years, fires in tropical forests and peatlands in equatorial Asia create large regional smoke clouds. We characterized the sensitivity of these clouds to regional drought, and we investigated their effects on climate by using an atmospheric general circulation model. Satellite observations during 2000–2006 indicated that El Niño-induced regional drought led to increases in fire emissions and, consequently, increases in aerosol optical depths over Sumatra, Borneo and the surrounding ocean. Next, we used the Community Atmosphere Model (CAM) to investigate how climate responded to this forcing. We conducted two 30 year simulations in which monthly fire emissions were prescribed for either a high (El Niño, 1997) or low (La Niña, 2000) fire year using a satellite-derived time series of fire emissions. Our simulations included the direct and semi-direct effects of aerosols on the radiation budget within the model. We assessed the radiative and climate effects of anthropogenic fire by analyzing the differences between the high and low fire simulations. Fire aerosols reduced net shortwave radiation at the surface during August–October by 19.1±12.9 W m−2 (10%) in a region that encompassed most of Sumatra and Borneo (90° E–120° E, 5° S–5° N). The reductions in net shortwave radiation cooled sea surface temperatures (SSTs) and land surface temperatures by 0.5±0.3 and 0.4±0.2 °C during these months. Tropospheric heating from black carbon (BC) absorption averaged 20.5±9.3 W m−2 and was balanced by a reduction in latent heating. The combination of decreased SSTs and increased atmospheric heating reduced regional precipitation by 0.9±0.6 mm d−1 (10%). The vulnerability of ecosystems to fire was enhanced because the decreases in precipitation exceeded those for evapotranspiration. Together, the satellite and modeling results imply a possible positive feedback loop in which anthropogenic burning in the region intensifies drought stress during El Niño.
OMI and MODIS observations of the anomalous 2008–2009 Southern Hemisphere biomass burning seasons

Significant inter-annual variability of biomass burning was observed in South America over the 2007–2009 period. The 2007 number of fires detected from space in South America, as well as the magnitude of the atmospheric aerosol load resulting from fire activity, was the largest over the last ten years. The huge 2007 increase in fire activity was followed by large reductions in the 2008 and 2009 burning seasons. Large drops of the atmospheric load of carbonaceous aerosols over the subcontinent, relative to previous years, was registered in 2008 and 2009 by the OMI sensor onboard the Aura platform, and the MODIS sensors on the Terra and Aqua satellites. The 2009 fire season in South America was the least active of the last ten years. Satellite observations of fire statistics, precipitation, and aerosol optical depth data were used to analyze the fire season over South America and Central Africa during the last ten years to understand the factors that led to the 2007 and 2009 extremes. An analysis of precipitation anomaly data shows that the largest 6-month (May–October) precipitation deficit of the last ten years in South America occurred during 2007. The same analysis indicates that in 2009, this region experienced the largest excess precipitation of the decade. Since precipitation is the most important meteorological factor controlling biomass burning activity, it can be concluded that the 2007 maximum and 2009 minimum in fire activity and aerosol load were driven by the observed levels of precipitation. Analysis of the precipitation record, however, does not explain the extremely low 2008 biomass burning activity. Although the 2008 precipitation deficit was similar in magnitude to the one that in 2005 contributed to the second most intense biomass burning season in the last ten years, the 2008 fire season was surprisingly weak. The combined analysis of satellite data on atmospheric aerosol load, fire counts and precipitation strongly suggests that the observed 2008 decline in aerosol load and fire activity in South America was heavily influenced by conditions other than meteorological factors.