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Technical note: The new comprehensive atmospheric chemistry module MECCA

In this technical note we present the multi-purpose atmospheric chemistry model MECCA. Owing to its versatility and modular structure, it can be used for tropospheric as well as stratospheric chemistry calculations. Extending the code to other domains (e.g. mesospheric or oceanic chemistry) is easily possible. MECCA contains a comprehensive atmospheric reaction mechanism that currently includes: 1) the basic O3, CH4, HOx, and NOx chemistry, 2) non-methane hydrocarbon (NMHC) chemistry, 3) halogen (Cl, Br, I) chemistry, and 4) sulfur chemistry. Not only gas-phase chemistry but also aqueous-phase and heterogeneous reactions are considered. Arbitrary subsets of the comprehensive mechanism can be selected according to the research objectives. The program code resulting from the chemical mechanism can easily be used in any model, from a simple box model to a comprehensive global general circulation model.
Commentary on cloud modelling and the mass accommodation coefficient of water

The mass accommodation coefficient of water is a quantity for which different experimental techniques have yielded conflicting values in the range 0.04-1. From the viewpoint of cloud modelling, this is an unfortunate situation, since the value of the mass accommodation coefficient affects the model results, e.g. the number concentration of activated cloud droplets. In this commentary we note that in cloud modelling, the primary quantity of interest is the droplet growth rate rather than the mass accommodation coefficient, and that experimental investigations of droplet growth rates provide more direct verification of cloud models than do measurements of the mass accommodation coefficient. Furthermore, we argue that the droplet growth rates calculated in cloud model studies are consistent with experimental results obtained so far only if a mass accommodation coefficient of unity is applied.
A comparison of new measurements of total monoterpene flux with improved measurements of speciated monoterpene flux

Many monoterpenes have been identified in forest emissions using gas chromatography (GC). Until now, it has been impossible to determine whether all monoterpenes are appropriately measured using GC techniques. We used a proton transfer reaction mass spectrometer (PTR-MS) coupled with the eddy covariance (EC) technique to measure mixing ratios and fluxes of total monoterpenes above a ponderosa pine plantation. We compared PTR-MS-EC results with simultaneous measurements of eight speciated monoterpenes, β-pinene, α-pinene, 3-carene, d-limonene, β-phellandrene, α-terpinene, camphene, and terpinolene, made with an automated, in situ gas chromatograph with flame ionization detectors (GC-FID), coupled to a relaxed eddy accumulation system (REA). Monoterpene mixing ratios and fluxes measured by PTR-MS averaged 30±2.3% and 31±9.2% larger than by GC-FID, with larger mixing ratio discrepancies between the two techniques at night than during the day. Two unidentified peaks that correlated with β-pinene were resolved in the chromatograms and completely accounted for the daytime difference and reduced the nighttime mixing ratio difference to 20±2.9%. Measurements of total monoterpenes by PTR-MS-EC indicated that GC-FID-REA measured the common, longer-lived monoterpenes well, but that additional terpenes were emitted from the ecosystem that represented an important contribution to the total mixing ratio above the forest at night.
Eddy covariance flux measurements of biogenic VOCs during ECHO 2003 using proton transfer reaction mass spectrometry

Within the framework of the AFO 2000 project ECHO, two PTR-MS instruments were operated in combination with sonic anemometers to determine biogenic VOC fluxes from a mixed deciduous forest site in North-Western Germany. The measurement site was characterised by a forest of inhomogeneous composition, complex canopy structure, limited extension in certain wind directions and frequent calm wind conditions during night time. The eddy covariance (EC) technique was applied since it represents the most direct flux measurement approach on the canopy scale and is, therefore, least susceptible to these non-ideal conditions. A specific flux calculation method was used to account for the sequential multi-component PTR-MS measurements and allowing an individual delay time adjustment as well as a rigorous quality control based on cospectral analysis. The validated flux results are consistent with light and temperature dependent emissions of isoprene and monoterpenes from this forest, with average daytime emissions of 0.94 and 0.3µg m-2s-1, respectively. Emissions of methanol reached on average 0.087µg m-2s-1 during daytime, but fluxes were too small to be detected during night time. Upward fluxes of the isoprene oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) were also found, being two orders of magnitude lower than those of isoprene. Calculations with an analytical footprint model indicate that the observed isoprene fluxes correlate with the fraction of oaks within the footprints of the flux measurement.
Actinometric measurements of NO2 photolysis frequencies in the atmosphere simulation chamber SAPHIR

The simulation chamber SAPHIR at Forschungszentrum Jülich has UV permeable teflon walls facilitating atmospheric photochemistry studies under the influence of natural sunlight. Because the internal radiation field is strongly affected by construction elements, we use external, radiometric measurements of spectral actinic flux and a model to calculate mean photolysis frequencies for the chamber volume Bohn04B. In this work we determine NO2 photolysis frequencies j(NO2) within SAPHIR using chemical actinometry by injecting NO2 and observing the chemical composition during illumination under various external conditions. In addition to a photo-stationary approach, a time-dependent method was developed to analyse the data. These measurements had two purposes. Firstly, to check the model predictions with respect to diurnal and seasonal variations in the presence of direct sunlight and secondly to obtain an absolute calibration factor for the combined radiometry-model approach. We obtain a linear correlation between calculated and actinometric j(NO2). A calibration factor of 1.34±0.10 is determined, independent of conditions in good approximation. This factor is in line with expectations and can be rationalised by internal reflections within the chamber. Taking into account the uncertainty of the actinometric j(NO2), an accuracy of 13% is estimated for the determination of j(NO2) in SAPHIR. In separate dark experiments a rate constant of (1.93±0.12)x10-14 cm3 s-1 was determined for the NO+O3 reaction at 298K using analytical and numerical methods of data analysis.
To what extent can aerosol water explain the discrepancy between model calculated and gravimetric PM10 and PM2.5?

Inter-comparisons of European air quality models show that regional transport models, including the EMEP (Co-operative Programme for monitoring and evaluation of the long-range transmission of air pollutants in Europe) aerosol model, tend to underestimate the observed concentrations of PM10 and PM2.5. Obviously, an accurate representation of the individual aerosol constituents is a prerequisite for adequate calculation of PM concentrations. On the other hand, available measurements on the chemical characterization of ambient particles reveal that full chemical PM mass closure is rarely achieved. The fraction unaccounted for by chemical analysis can comprise as much as 30-40% of gravimetric PM10 or PM2.5 mass. The unaccounted PM mass can partly be due to non-C atoms in organic aerosols and/or due to sampling and measurement artefacts. Moreover, a part of the unaccounted PM mass is likely to consist of water associated with particles. Thus, the gravimetrically measured particle mass does not necessarily represent dry PM10 and PM2.5 mass. This is thought to be one of the reasons for models under-prediction of observed PM, if calculated dry PM10 and PM2.5 concentrations are compared with measurements. The EMEP aerosol model has been used to study to what extent particle-bound water can explain the chemically unidentified PM mass in filter-based particle samples. Water content of PM2.5 and PM10 has been estimated with the model for temperature 20°C and relative humidity 50%, which are conditions required for equilibration of dust-loaded filters according to the Reference method recommended by the European Committee for Standardization (CEN). Model calculations for Europe show that, depending on particle composition, particle-bound water constitutes 20-35% of the annual mean PM10 and PM2.5 concentrations, which is consistent with existing experimental estimates. At two Austrian sites, in Vienna and Streithofen, where daily measurements of PM2.5 mass and chemical composition are available, calculated PM2.5 water content is found to be about 75-80% of the undetermined PM2.5 mass and there is correlation between them. Furthermore, accounting for aerosol water has improved the agreement between modelled and measured daily PM2.5 concentrations, whilst model calculated dry PM2.5 concentrations appear to agree quite well with the total identified PM2.5 mass. No information on the composition of PM measured at EMEP sites is presently available. Given that PM10 and PM2.5 concentrations are measured at EMEP stations with gravimetric methods they are likely to contain water. We show that the levels of modelled PM10 and PM2.5 concentrations with aerosol water included agree with measurements better than dry PM concentrations. As expected, the spatial correlation has not changed significantly, whereas the temporal correlation of daily PM10 and PM2.5 with monitoring data has slightly improved at most of the EMEP sites. Our results suggest that aerosol water should be accounted for in modelled PM10 and PM2.5 when compared with filter-based gravimetric measurements.
Microphysics and heterogeneous chemistry in aircraft plumes - high sensitivity on local meteorology and atmospheric composition

An aircraft plume model has been developed on the basis of two coupled trajectory box models. Two boxes, one for plume and one for background conditions, are coupled by means of a mixing parameterization based on turbulence theory. The model considers comprehensive gas phase chemistry for the tropopause region including acetone, ethane and their oxidation products. Heterogeneous halogen, N2O5 and HOx chemistry on various types of background and aircraft-induced aerosols (liquid and ice) is considered, using state-of-the-art solubility dependent uptake coefficients for liquid phase reactions. The microphysical scheme allows for coagulation, gas-diffusive particle growth and evaporation, so that the particle development from 1s after emission to several days can be simulated. Model results are shown, studying emissions into the upper troposphere as well as into the lowermost stratosphere for contrail and non-contrail conditions. We show the microphysical and chemical evolution of spreading plumes and use the concept of mean plume encounter time, tl, to define effective emission and perturbation indices (EEIs and EPIs) for the North Atlantic Flight Corridor (NAFC) showing EEI(NOy) and EPI(O3) for various background conditions, such as relative humidity, local time of emission, and seasonal variations. Our results show a high sensitivity of EEI and EPIs on the exact conditions under which emissions take place. The difference of EEIs with and without considering plume processes indicates that these processes cannot be neglected.
Increased Northern Hemispheric carbon monoxide burden in the troposphere in 2002 and 2003 detected from the ground and from space

Carbon monoxide total column amounts in the atmosphere have been measured in the High Northern Hemisphere (30°-90° N, HNH) between January 2002 and December 2003 using infrared spectrometers of high and moderate resolution and the Sun as a light source. They were compared to ground-level CO mixing ratios and to total column amounts measured from space by the Terra/MOPITT instrument. All these data reveal increased CO abundances in 2002-2003 in comparison to the unperturbed 2000-2001 period. Maximum anomalies were observed in September 2002 and August 2003. Using a simple two-box model, the corresponding annual CO emission anomalies (referenced to 2000-2001 period) have been found equal to 95Tg in 2002 and 130Tg in 2003, thus close to those for 1996 and 1998. A good correlation with hot spots detected by a satellite radiometer allows one to assume strong boreal forest fires, occurred mainly in Russia, as a source of the increased CO burdens.
Stratospheric temperatures and tracer transport in a nudged 4-year middle atmosphere GCM simulation

We have performed a 4-year simulation with the Middle Atmosphere General Circulation Model MAECHAM5/MESSy, while slightly nudging the model’s meteorology in the free troposphere (below 113 hPa) towards ECMWF analyses. We show that the nudging 5 technique, which leaves the middle atmosphere almost entirely free, enables comparisons with synoptic observations. The model successfully reproduces many specific features of the interannual variability, including details of the Antarctic vortex structure. In the Arctic, the model captures general features of the interannual variability, but falls short in reproducing the timing of sudden stratospheric warmings. A 10 detailed comparison of the nudged model simulations with ECMWF data shows that the model simulates realistic stratospheric temperature distributions and variabilities, including the temperature minima in the Antarctic vortex. Some small (a few K) model biases were also identified, including a summer cold bias at both poles, and a general cold bias in the lower stratosphere, most pronounced in midlatitudes. A comparison 15 of tracer distributions with HALOE observations shows that the model successfully reproduces specific aspects of the instantaneous circulation. The main tracer transport deficiencies occur in the polar lowermost stratosphere. These are related to the tropopause altitude as well as the tracer advection scheme and model resolution. The additional nudging of equatorial zonal winds, forcing the quasi-biennial oscillation, sig20 nificantly improves stratospheric temperatures and tracer distributions.
Measurements of total odd nitrogen (NOy) aboard MOZAIC in-service aircraft: instrument design, operation and performance

A small system for the unattended measurement of total odd nitrogen (NOy, i.e., the sum of NO and its atmospheric oxidation products) aboard civil in-service aircraft in the framework of MOZAIC is described. The instrument employs the detection of NO by its chemiluminescence with O3 in combination with catalytic conversion of the other NOy compounds to NO at 300°C on a gold surface in the presence of H2. The instrument has a sensitivity of 0.4-0.7cps/ppt and is designed for unattended operation during 1-2 service cycles of the aircraft (400-800 flight hours). The total weight is 50kg, including calibration system, compressed gases, mounting, and safety measures. The layout and inlet configuration are governed by requirements due to the certification for passenger aircraft. Laboratory tests are described regarding the conversion efficiency for NO2 and HNO3 (both >98%). Interference by non-NOy species is <1% for CH3CN and NH3, <5x10-5% for N2O (corresponding to <0.2ppt fake NOy from ambient N2O) and 100% for HCN. The time response of the instrument is <1s (90% change) for NO2. The response for HNO3 is nonlinear: 20s for 67%, 60s for 80%, and 150s for 90% response, respectively.