Items

Advanced search

The spring 2011 final stratospheric warming above Eureka: anomalous dynamics and chemistry

In spring 2011, the Arctic polar vortex was stronger than in any other year on record. As the polar vortex started to break up in April, ozone and NO2 columns were measured with UV-visible spectrometers above the Polar Environment Atmospheric Research Laboratory (PEARL) in Eureka, Canada (80.05° N, 86.42° W) using the differential optical absorption spectroscopy (DOAS) technique. These ground-based column measurements were complemented by Ozone Monitoring Instrument (OMI) and Optical Spectrograph and Infra-Red Imager System (OSIRIS) satellite measurements, Global Modeling Initiative (GMI) simulations, and meteorological quantities. On 8 April 2011, NO2 columns above PEARL from the DOAS, OMI, and GMI datasets were approximately twice as large as in previous years. On this day, temperatures and ozone volume mixing ratios above Eureka were high, suggesting enhanced chemical production of NO2 from NO. Additionally, GMI NOx (NO + NO2) and N2O fields suggest that downward transport along the vortex edge and horizontal transport from lower latitudes also contributed to the enhanced NO2. The anticyclone that transported lower-latitude NOx above PEARL became frozen-in and persisted in dynamical and GMI N2O fields until the end of the measurement period on 31 May 2011. Ozone isolated within this frozen-in anticyclone (FrIAC) in the middle stratosphere was lost due to reactions with the enhanced NOx. Below the FrIAC (from the tropopause to 700 K), NOx driven ozone loss above Eureka was larger than in previous years, according to GMI monthly average ozone loss rates. Using the passive tracer technique, with passive ozone profiles from the Lagrangian Chemistry and Transport Model, ATLAS, ozone losses since 1 December 2010 were calculated at 600 K. In the air mass that was above Eureka on 20 May 2011, ozone losses reached 4.2 parts per million by volume (ppmv) (58%) and 4.4 ppmv (61%), when calculated using GMI and OSIRIS ozone profiles, respectively. This gas-phase ozone loss led to a more rapid decrease in ozone column amounts above Eureka in April/May 2011 compared with previous years. Ground-based, OMI, and GMI ozone total columns all decreased by more than 100 DU from 15 April to 20 May. Two lows in the ozone columns were also investigated and were attributed to a vortex remnant passing above Eureka at ~500 K on 12/13 May and an ozone mini-hole on 22/23 May.
Assessment of the Level-3 MODIS daily aerosol optical depth in the context of surface solar radiation and numerical weather modeling

The daily Level-3 MODIS aerosol optical depth (AOD) product is a global daily spatial aggregation of the Level-2 MODIS AOD (10-km spatial resolution) into a regular grid with a resolution of 1° × 1°. It offers interesting characteristics for surface solar radiation and numerical weather modeling applications. However, most of the validation efforts so far have focused on Level-2 products and only rarely on Level 3. In this contribution, we compare the Level-3 Collection 5.1 MODIS AOD dataset from the Terra satellite available since 2000 against observed daily AOD values at 550 nm from more than 500 AERONET ground stations around the globe. Overall, the mean error of the dataset is 0.03 (17%, relative to the mean ground-observed AOD), with a root mean square error of 0.14 (73%, relative to the same), but these errors are also found highly dependent on geographical region. We propose new functions for the expected error of the Level-3 AOD, as well as for both its mean error and its standard deviation. Additionally, we investigate the role of pixel count vis-à-vis the reliability of the AOD estimates, and also explore to what extent the spatial aggregation from Level 2 to Level 3 influences the total uncertainty in the Level-3 AOD. Finally, we use a radiative transfer model to investigate how the Level-3 AOD uncertainty propagates into the calculated direct normal and global horizontal irradiances.
Stratospheric impact on tropospheric ozone variability and trends: 1990–2009

The influence of stratospheric ozone on the interannual variability and trends in tropospheric ozone is evaluated between 30 and 90° N from 1990–2009 using ozone measurements and a global chemical transport model, the Community Atmospheric Model with chemistry (CAM-chem). Long-term measurements from ozonesondes, at 150 and 500 hPa, and the Measurements of OZone and water vapour by in-service Airbus aircraft programme (MOZAIC), at 500 hPa, are analyzed over Japan, Canada, the Eastern US and Northern and Central Europe. The measurements generally emphasize northern latitudes, although the simulation suggests that measurements over the Canadian, Northern and Central European regions are representative of the large-scale interannual ozone variability from 30 to 90° N at 500 hPa. CAM-chem is run with input meteorology from the National Center for Environmental Prediction; a tagging methodology is used to identify the stratospheric contribution to tropospheric ozone concentrations. A variant of the synthetic ozone tracer (synoz) is used to represent stratospheric ozone. Both the model and measurements indicate that on large spatial scales stratospheric interannual ozone variability drives significant tropospheric variability at 500 hPa and the surface. In particular, the simulation and the measurements suggest large stratospheric influence at the surface sites of Mace Head (Ireland) and Jungfraujoch (Switzerland) as well as many 500 hPa measurement locations. Both the measurements and simulation suggest the stratosphere has contributed to tropospheric ozone trends. In many locations between 30–90° N 500 hPa ozone significantly increased from 1990–2000, but has leveled off since (from 2000–2009). The simulated global ozone budget suggests global stratosphere-troposphere exchange increased in 1998–1999 in association with a global ozone anomaly. Discrepancies between the simulated and measured ozone budget include a large underestimation of measured ozone variability and discrepancies in long-term stratospheric ozone trends. This suggests the need for more sophisticated simulations including better representations of stratospheric chemistry and circulation.
The Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS): model description and application to a temperate deciduous forest canopy

Forest canopies are primary emission sources of biogenic volatile organic compounds (BVOCs) and have the potential to significantly influence the formation and distribution of secondary organic aerosol (SOA) mass. Biogenically-derived SOA formed as a result of emissions from the widespread forests across the globe may affect air quality in populated areas, degrade atmospheric visibility, and affect climate through direct and indirect forcings. In an effort to better understand the formation of SOA mass from forest emissions, a 1-D column model of the multiphase physical and chemical processes occurring within and just above a vegetative canopy is being developed. An initial, gas-phase-only version of this model, the Atmospheric Chemistry and Canopy Exchange Simulation System (ACCESS), includes processes accounting for the emission of BVOCs from the canopy, turbulent vertical transport within and above the canopy and throughout the height of the planetary boundary layer (PBL), near-explicit representation of chemical transformations, mixing with the background atmosphere and bi-directional exchange between the atmosphere and canopy and the atmosphere and forest floor. The model formulation of ACCESS is described in detail and results are presented for an initial application of the modeling system to Walker Branch Watershed, an isoprene-emission-dominated forest canopy in the southeastern United States which has been the focal point for previous chemical and micrometeorological studies. Model results of isoprene profiles and fluxes are found to be consistent with previous measurements made at the simulated site and with other measurements made in and above mixed deciduous forests in the southeastern United States. Sensitivity experiments are presented which explore how canopy concentrations and fluxes of gas-phase precursors of SOA are affected by background anthropogenic nitrogen oxides (NOx). Results from these experiments suggest that the level of ambient NOx influences the pathways by which SOA is formed by affecting the relative magnitudes and fluxes of isoprene oxidation products emitted from the canopy. Future versions of the ACCESS model are planned to be multiphase, including gas- and aerosol-phase chemical and physical processes, to more fully explore these preliminary results.
Mass-based hygroscopicity parameter interaction model and measurement of atmospheric aerosol water uptake

In this study we derive and apply a mass-based hygroscopicity parameter interaction model for efficient description of concentration-dependent water uptake by atmospheric aerosol particles with complex chemical composition. The model approach builds on the single hygroscopicity parameter model of Petters and Kreidenweis (2007). We introduce an observable mass-based hygroscopicity parameter κm which can be deconvoluted into a dilute hygroscopicity parameter (κm0) and additional self- and cross-interaction parameters describing non-ideal solution behavior and concentration dependencies of single- and multi-component systems. For reference aerosol samples of sodium chloride and ammonium sulfate, the κm-interaction model (KIM) captures the experimentally observed concentration and humidity dependence of the hygroscopicity parameter and is in good agreement with an accurate reference model based on the Pitzer ion-interaction approach (Aerosol Inorganic Model, AIM). Experimental results for pure organic particles (malonic acid, levoglucosan) and for mixed organic-inorganic particles (malonic acid – ammonium sulfate) are also well reproduced by KIM, taking into account apparent or equilibrium solubilities for stepwise or gradual deliquescence and efflorescence transitions. The mixed organic-inorganic particles as well as atmospheric aerosol samples exhibit three distinctly different regimes of hygroscopicity: (I) a quasi-eutonic deliquescence & efflorescence regime at low-humidity where substances are just partly dissolved and exist also in a non-dissolved phase, (II) a gradual deliquescence & efflorescence regime at intermediate humidity where different solutes undergo gradual dissolution or solidification in the aqueous phase; and (III) a dilute regime at high humidity where the solutes are fully dissolved approaching their dilute hygroscopicity. For atmospheric aerosol samples collected from boreal rural air and from pristine tropical rainforest air (secondary organic aerosol) we present first mass-based measurements of water uptake over a wide range of relative humidity (1–99.4%) obtained with a new filter-based differential hygroscopicity analyzer (FDHA) technique. For these samples the concentration dependence of κm can be described by a simple KIM model equation based on observable mass growth factors and a total of only six fit parameters summarizing the combined effects of the dilute hygroscopicity parameters, self- and cross-interaction parameters, and solubilities of all involved chemical components. One of the fit parameters represents κm0 and can be used to predict critical dry diameters for the activation of cloud condensation nuclei (CCN) as a function of water vapor supersaturation according to Köhler theory. For sodium chloride and ammonium sulfate reference particles as well as for pristine rainforest aerosols consisting mostly of secondary organic matter, we obtained good agreement between the KIM predictions and measurement data of CCN activation. The application of KIM and mass-based measurement techniques shall help to bridge gaps in the current understanding of water uptake by atmospheric aerosols: (1) the gap between hygroscopicity parameters determined by hygroscopic growth measurements under sub-saturated conditions and by CCN activation measurements at water vapor supersaturation, and (2) the gap between the results of simplified single parameter models widely used in atmospheric or climate science and the results of complex multi-parameter ion- and molecule-interaction models frequently used in physical chemistry and solution thermodynamics (e.g., AIM, E-AIM, ADDEM, UNIFAC, AIOMFAC).
Effect of photochemical ageing on the ice nucleation properties of diesel and wood burning particles

A measurement campaign (IMBALANCE) conducted in 2009 was aimed at characterizing the physical and chemical properties of freshly emitted and photochemically aged combustion particles emitted from a log wood burner and diesel vehicles: a EURO3 Opel Astra with a diesel oxidation catalyst (DOC) but no particle filter and a EURO2 Volkswagen Transporter TDI Syncro without emission aftertreatment. Ice nucleation experiments in the deposition and condensation freezing modes were conducted with the Portable Ice Nucleation Chamber (PINC) at three nominal temperatures, −30 °C, −35 °C and −40 °C. Freshly emitted diesel particles showed ice formation only at −40 °C in the deposition mode at 137% relative humidity with respect to ice (RHi) and 92% relative humidity with respect to water (RHw), and photochemical ageing did not play a role in modifying their ice nucleation behaviour. Only one diesel experiment where α-pinene was added for the ageing process, showed an ice nucleation enhancement at −35 °C. Wood burning particles also act as ice nuclei (IN) at −40 °C in the deposition mode at the same conditions as for diesel particles and photochemical ageing also did not alter the ice formation properties of the wood burning particles. Unlike diesel particles, wood burning particles form ice via condensation freezing at −35 °C whereas no ice nucleation was observed at −30 °C. Photochemical ageing did not affect the ice nucleation ability of the diesel and wood burning particles at the three different temperatures investigated but a broader range of temperatures below −40 °C need to be investigated in order to draw an overall conclusion on the effect of photochemical ageing on deposition/condensation ice nucleation across the entire temperature range relevant to cold clouds.
Technical Note: New methodology for measuring viscosities in small volumes characteristic of environmental chamber particle samples

Herein, a method for the determination of viscosities of small sample volumes is introduced, with important implications for the viscosity determination of particle samples from environmental chambers (used to simulate atmospheric conditions). The amount of sample needed is < 1 μl, and the technique is capable of determining viscosities (η) ranging between 10−3 and 103 Pascal seconds (Pa s) in samples that cover a range of chemical properties and with real-time relative humidity and temperature control; hence, the technique should be well-suited for determining the viscosities, under atmospherically relevant conditions, of particles collected from environmental chambers. In this technique, supermicron particles are first deposited on an inert hydrophobic substrate. Then, insoluble beads (~1 μm in diameter) are embedded in the particles. Next, a flow of gas is introduced over the particles, which generates a shear stress on the particle surfaces. The sample responds to this shear stress by generating internal circulations, which are quantified with an optical microscope by monitoring the movement of the beads. The rate of internal circulation is shown to be a function of particle viscosity but independent of the particle material for a wide range of organic and organic-water samples. A calibration curve is constructed from the experimental data that relates the rate of internal circulation to particle viscosity, and this calibration curve is successfully used to predict viscosities in multicomponent organic mixtures.
The influence of biomass burning on the global distribution of selected non-methane organic compounds

Forests fires are a significant source of chemicals to the atmosphere including numerous non-methane organic compounds (NMOCs). We report airborne measurement of hydrocarbons, acetone and methanol from >500 whole air samples collected over Eastern Canada, including interceptions of several different boreal biomass burning plumes. From these and concurrent measurements of carbon monoxide (CO) we derive fire emission ratios for 29 different organic species relative to the emission of CO. These range from 8.9 ± 3.2 ppt ppb−1 CO for methanol to 0.007 ± 0.004 ppt ppb−1 CO for cyclopentane. The ratios are in good to excellent agreement with literature values. Using the GEOS-Chem global 3-D chemical transport model (CTM) we show the influence of biomass burning on the global distributions of benzene, toluene, ethene and propene (species which are controlled for air quality purposes and sometimes used as indicative tracers of anthropogenic activity). Using our observationally derived emission ratios and the GEOS-Chem CTM, we show that biomass burning can be the largest fractional contributor to observed benzene, toluene, ethene and propene levels in many global locations. The widespread biomass burning contribution to atmospheric benzene, a heavily regulated air pollutant, suggests that pragmatic approaches are needed when setting air quality targets as tailpipe and solvent emissions decline in developed countries. We subsequently determine the extent to which the 28 global-status World Meteorological Organisation – Global Atmosphere Watch stations worldwide are influenced by biomass burning sourced benzene, toluene, ethene and propene as compared to their exposure to anthropogenic emissions.
Decadal record of satellite carbon monoxide observations

Atmospheric carbon monoxide (CO) distributions are controlled by anthropogenic emissions, biomass burning, transport and oxidation by reaction with the hydroxyl radical (OH). Quantifying trends in CO is therefore important for understanding changes related to all of these contributions. Here we present a comprehensive record of satellite observations from 2000 through 2011 of total column CO using the available measurements from nadir-viewing thermal infrared instruments: MOPITT, AIRS, TES and IASI. We examine trends for CO in the Northern and Southern Hemispheres along with regional trends for Eastern China, Eastern USA, Europe and India. We find that all the satellite observations are consistent with a modest decreasing trend ~ −1 % yr−1 in total column CO over the Northern Hemisphere for this time period and a less significant, but still decreasing trend in the Southern Hemisphere. Although decreasing trends in the United States and Europe have been observed from surface CO measurements, we also find a decrease in CO over E. China that, to our knowledge, has not been reported previously. Some of the interannual variability in the observations can be explained by global fire emissions, but the overall decrease needs further study to understand the implications for changes in anthropogenic emissions.
Total sulphate vs. sulphuric acid monomer in nucleation studies: which represents the "true" concentration?

Sulphuric acid is known to be a key component for atmospheric nucleation. Precise determination of sulphuric acid concentration is crucial factor for prediction of nucleation rates and subsequent growth. In our study, we have noticed a substantial discrepancy between sulphuric acid monomer and total sulphate concentrations measured from the same source of sulphuric acid vapour. The discrepancy of about one to two orders of magnitude was found with similar formation rates. The reason for this difference is not yet clear and it can have great impact on predicting atmospheric nucleation rates as well as growth rates. To investigate this discrepancy and its effect on nucleation, a method of thermally controlled saturator filled with pure sulphuric acid (~97%) for production of sulphuric acid vapour is introduced and tested. Sulphuric acid-water nucleation experiment was done using a laminar flow tube. Two independent methods of mass spectrometry and online ion chromatography were used for detecting sulphuric acid concentrations. The results are compared to our previous results, where a method of evaporating weak sulphuric acid-water solution droplets in a furnace was used to produce sulphuric acid vapour (Brus et al., 2010, 2011). Measured sulphuric acid concentrations are compared to theoretical prediction calculated using vapour pressure and simple mixing law. The calculated prediction of sulphuric acid concentrations agrees very well with the measured values when total sulphate is considered. Sulphuric acid monomer concentration was found to be about two orders of magnitude lower than the prediction, but with similar temperature dependency as the prediction and the results obtained with ion chromatograph method. Formation rates agree well when compared to our previous results with both sulphuric acid detection and sulphuric acid production methods separately.