Items

Advanced search

Photochemical modelling in the Po basin with focus on formaldehyde and ozone

As part of the EU project FORMAT (Formaldehyde as a Tracer of Oxidation in the Troposphere), a field campaign was carried out in the vicinity of Milan during the summer of 2002. Results from a 3-D regional chemical transport model (NILU RCTM) were used to interpret the observations focusing primarily on HCHO and ozone. The performance of the model was assessed by comparing model results with ground based and aircraft measurements. The model results show good agreement with surface measurements, and the model is able to reproduce the photochemical episodes during fair weather days. The comparison indicates that the model can represent well the HCHO concentrations as well as their temporal and spatial variability. The relationship between HCHO and (O3×H2O) was used to validate the model ability to predict the HCHO concentrations. Further analysis revealed the importance of the representativeness of different instruments: in-situ concentrations might be locally enhanced by emissions, while long path measurements over a forest can be influenced by rapid formation of HCHO from isoprene. The model is able to capture the plume from the city of Milan and the modelled levels agree generally well with the aircraft measurements, although the wind fields used in the model can lead to a displacement of the ozone plume. During the campaign period, O3 levels were seldom higher than 80 ppb, the peak surface ozone maxima reached 90 ppb. Those relatively low values can be explained by low emissions during the August vacation and unstable weather conditions in this period. The modelled ΔO3/ΔNOz slope at Alzate of 5.1 agrees well with the measured slope of 4.9.
High resolution vertical distributions of NO3 and N2O5 through the nocturnal boundary layer

The shallow mixing depth and vertical stratification of the lowest levels of the atmosphere at night has implications for the chemistry of nitrogen oxides emitted from the surface. Here we report vertical profiles of NO3, N2O5 and O3 measured from in-situ instruments on a movable carriage on a 300 m tower. The study offers high-resolution (<1 m) vertical distributions of both NO3 and N2O5 and shows that the nocturnal mixing ratios of these compounds vary widely over short vertical distance scales (10 m or less). Furthermore, there are systematic differences in the steady state lifetimes of NO3 and N2O5 and in the partitioning among nitrogen oxides between different near-surface layers. These differences imply that NO3 and N2O5 occupy distinct chemical regimes as a function of altitude, potentially serving as sinks for nitrogen oxides and O3 near the surface but as reservoirs of NOx and O3 aloft.
Free radical modelling studies during the UK TORCH Campaign in Summer 2003

The Tropospheric ORganic CHemistry experiment (TORCH) took place during the heatwave of summer 2003 at Writtle College, a site 2 miles west of Chelmsford in Essex and 25 miles north east of London. The experiment was one of the most highly instrumented to date. A combination of a large number of days of simultaneous, collocated measurements, a consequent wealth of model constraints and a highly detailed chemical mechanism, allowed the atmospheric chemistry of this site to be studied in detail. Between 25 July and 31 August, the concentrations of the hydroxyl radical and the hydroperoxy radical were measured using laser-induced fluorescence at low pressure and the sum of peroxy radicals was measured using the peroxy radical chemical amplifier technique. The concentrations of the radical species were predicted using a zero-dimensional box model based on the Master Chemical Mechanism version 3.1, which was constrained with the observed concentrations of relatively long-lived species. The model included a detailed parameterisation to account for heterogeneous loss of hydroperoxy radicals onto aerosol particles. Quantile-quantile plots were used to assess the model performance in respect of the measured radical concentrations. On average, measured hydroxyl radical concentrations were over-predicted by 24%. Modelled and measured hydroperoxy radical concentrations agreed very well, with the model over-predicting on average by only 7%. The sum of peroxy radicals was under-predicted when compared with the respective measurements by 22%. Initiation via OH was dominated by the reactions of excited oxygen atoms with water, nitrous acid photolysis and the ozone reaction with alkene species. Photolysis of aldehyde species was the main route for initiation via HO2 and RO2. Termination, under all conditions, primarily involved reactions with NOx for OH and heterogeneous chemistry on aerosol surfaces for HO2. The OH chain length varied between 2 and 8 cycles, the longer chain lengths occurring before and after the most polluted part of the campaign. Peak local ozone production of 17 ppb hr−1 occurred on 3 and 5 August, signifying the importance of local chemical processes to ozone production on these days. On the whole, agreement between model and measured radicals is good, giving confidence that our understanding of atmospheres influenced by nearby urban sources is adequate.
Identification and classification of the formation of intermediate ions measured in boreal forest

We have measured the size distributions of air ions (0.42–7.5 nm in diameter) with the Balanced Scanning Mobility Analyzer in boreal forest, in Southern Finland since spring 2003. The size range covers the size range of cluster ions (approximately 0.42–1.6 nm) and naturally charged nanometre aerosol particles (1.6–7.5 nm) or intermediate air ions. Based on the measurements from April 2003 to March 2006 we studied the characteristics of charged aerosol particle formation by classifying each day either as a particle formation event, undefined or non-event day. The principal of the classification, as well as the statistical description of the charged aerosol particle formation events are given. We found in total 270 (26% of the analysed days) and 226 (22% of the analysed days) particle formation days for negative and positive intermediate ions, respectively. For negatively charged particles we classified 411 (40% of the analysed days) undefined and 348 (34% of the analysed days) non-event days whereas for positively charged particles 343 (33% of the analysed days) undefined and 460 (45% of the analysed days) non-event days. The results were compared with the ordinary classification based on the Differential Mobility Particle Sizer (DMPS) measurements carried out at the same place. The above-presented values differed slightly from that found from the DMPS data, with a lower particle diameter of 3 nm. In addition, we have found the rain-induced intermediate ion bursts frequently. The rain effect was detected on 163 days by means of negative ions and on 105 days by positive ones. Another interesting phenomenon among the charged aerosol particles was the appearance and existence of intermediate ions during the snowfall. We observed this phenomenon 24 times with negatively charged particles and 21 times with positively charged ones during winter months (October–April). These intermediate air ions were seen during the snowfall and may be caused by ice crystals, although the origin of these intermediate ions is unclear at the moment.
Stationary planetary wave propagation in Northern Hemisphere winter – climatological analysis of the refractive index

The probability density on a height-meridional plane of negative refractive index squared f(nk2<0) is introduced as a new analysis tool to investigate the climatology of the propagation conditions of stationary planetary waves based on NCEP/NCAR reanalysis data for 44 Northern Hemisphere boreal winters (1958–2002). This analysis addresses the control of the atmospheric state on planetary wave propagation. It is found that not only the variability of atmospheric stability with altitudes, but also the variability with latitudes has significant influence on planetary wave propagation. Eliassen-Palm flux and divergence are also analyzed to investigate the eddy activities and forcing on zonal mean flow. Only the ultra-long planetary waves with zonal wave number 1, 2 and 3 are investigated. In Northern Hemisphere winter the atmosphere shows a large possibility for stationary planetary waves to propagate from the troposphere to the stratosphere. On the other hand, waves induce eddy momentum flux in the subtropical troposphere and eddy heat flux in the subpolar stratosphere. Waves also exert eddy momentum forcing on the mean flow in the troposphere and stratosphere at middle and high latitudes. A similar analysis is also performed for stratospheric strong and weak polar vortex regimes, respectively. Anomalies of stratospheric circulation affect planetary wave propagation and waves also play an important role in constructing and maintaining of interannual variations of stratospheric circulation.
Seasonal variability of measured ozone production efficiencies in the lower free troposphere of Central Europe

In this study we present the seasonal variability of ozone production efficiencies (EN), defined as the net number of ozone molecules produced per molecule of nitrogen oxides (nitrogen oxide (NO) + nitrogen dioxide (NO2)=NOx) oxidized to NOz (total reactive nitrogen (NOy)–NOx) determined from field measurements of a seven-year period (1998–2004) at the Swiss high-alpine research station Jungfraujoch (JFJ), 3580 m a.s.l. This dataset is a unique long-term data series of nitrogen levels in the free troposphere over Central Europe and hence it offers an excellent opportunity to perform such an analysis and provide further evidence to the photochemical origin of the ozone spring maximum at locations of the northern hemisphere distant from nearby pollution sources. Experimentally derived daily EN values have been selected for 571 days out of the 2557 days from 1998 to 2004, from which an average ozone production efficiency of 18.8±1.3 molecules of O3 produced per molecule of NOx oxidized was calculated. This value indicates the great potential and importance of photochemical ozone production in the free troposphere. The monthly means of experimentally derived daily EN values show a seasonal variation with lower values from May to August, which can be probably attributed to more efficient vertical transport of polluted air masses from the atmospheric boundary layer up to JFJ. In agreement, theoretically derived monthly EN values show similar seasonal variation. The ratio NOy/CO, a parameter to assess the aging process that has occurred in an air parcel, was used as a criterion to disaggregate the 571 selected days between undisturbed and disturbed free tropospheric (FT). The monthly means of experimentally derived EN values for the undisturbed FT conditions show a distinct seasonal cycle with higher values in the cold season from November to April. The EN values for undisturbed FT conditions are particularly higher than the respective monthly EN values for disturbed FT conditions from February to October. It should be noted that the monthly EN values of March (EN=35.8) and April (EN=34.9) are among the highest values throughout the year for undisturbed FT conditions at JFJ. These results highlight the key and possibly the dominant role for photochemistry in the observed build-up of tropospheric ozone in the winter-spring transition period.
Hygroscopic properties of ultrafine aerosol particles in the boreal forest: diurnal variation, solubility and the influence of sulfuric acid

The hygroscopic growth of aerosol particles present in a boreal forest was measured at a relative humidity of 88%. Simultaneously the gas phase concentration of sulfuric acid, a very hygroscopic compound, was monitored. The focus was mainly on days with new particle formation by nucleation. The measured hygroscopic growth factors (GF) correlated positively with the gaseous phase sulfuric acid concentrations. The smaller the particles, the stronger the correlation, with r=0.20 for 50 nm and r=0.50 for 10 nm particles. The increase in GF due to condensing sulfuric acid is expected to be larger for particles with initially smaller masses. During new particle formation, the changes in solubility of the new particles were calculated during their growth to Aitken mode sizes. As the modal diameter increased, the solubility of the particles decreased. This indicated that the initial particle growth was due to more hygroscopic compounds, whereas the later growth during the evening and night was mainly caused by less hygroscopic or even hydrophobic compounds. For all the measured sizes, a diurnal variation in GF was observed both during days with and without particle formation. The GF was lowest at around midnight, with a mean value of 1.12–1.24 depending on particle size and if new particle formation occurred during the day, and increased to 1.25–1.34 around noon. This can be tentatively explained by day- and nighttime gas-phase chemistry; different vapors will be present depending on the time of day, and through condensation these compounds will alter the hygroscopic properties of the particles in different ways.
Stable isotopes provide revised global limits of aerobic methane emissions from plants

Recently Keppler et al. (2006) discovered a surprising new source of methane – terrestrial plants under aerobic conditions, with an estimated global production of 62–236 Tg yr−1 by an unknown mechanism. This is ~10–40% of the annual total of methane entering the modern atmosphere and ~30–100% of annual methane entering the pre-industrial (0 to 1700 AD) atmosphere. Here we test this reported global production of methane from plants against ice core records of atmospheric methane concentration (CH4) and stable carbon isotope ratios (δ13CH4) over the last 2000 years. Our top-down approach determines that global plant emissions must be much lower than proposed by Keppler et al. (2006) during the last 2000 years and are likely to lie in the range 0–46 Tg yr−1 and 0–176 Tg yr−1 during the pre-industrial and modern eras, respectively.
Validation of MIPAS ClONO2 measurements

Altitude profiles of ClONO2 retrieved with the IMK (Institut für Meteorologie und Klimaforschung) science-oriented data processor from MIPAS/Envisat (Michelson Interferometer for Passive Atmospheric Sounding on Envisat) mid-infrared limb emission measurements between July 2002 and March 2004 have been validated by comparison with balloon-borne (Mark IV, FIRS2, MIPAS-B), airborne (MIPAS-STR), ground-based (Spitsbergen, Thule, Kiruna, Harestua, Jungfraujoch, Izaña, Wollongong, Lauder), and spaceborne (ACE-FTS) observations. With few exceptions we found very good agreement between these instruments and MIPAS with no evidence for any bias in most cases and altitude regions. For balloon-borne measurements typical absolute mean differences are below 0.05 ppbv over the whole altitude range from 10 to 39 km. In case of ACE-FTS observations mean differences are below 0.03 ppbv for observations below 26 km. Above this altitude the comparison with ACE-FTS is affected by the photochemically induced diurnal variation of ClONO2. Correction for this by use of a chemical transport model led to an overcompensation of the photochemical effect by up to 0.1 ppbv at altitudes of 30–35 km in case of MIPAS-ACE-FTS comparisons while for the balloon-borne observations no such inconsistency has been detected. The comparison of MIPAS derived total column amounts with ground-based observations revealed no significant bias in the MIPAS data. Mean differences between MIPAS and FTIR column abundances are 0.11±0.12×1014 cm−2 (1.0±1.1%) and −0.09±0.19×1014 cm−2 (−0.8±1.7%), depending on the coincidence criterion applied. χ2 tests have been performed to assess the combined precision estimates of MIPAS and the related instruments. When no exact coincidences were available as in case of MIPAS – FTIR or MIPAS – ACE-FTS comparisons it has been necessary to take into consideration a coincidence error term to account for χ2 deviations. From the resulting χ2 profiles there is no evidence for a systematic over/underestimation of the MIPAS random error analysis.
Technical Note: A numerical test-bed for detailed ice nucleation studies in the AIDA cloud simulation chamber

The AIDA (Aerosol Interactions and Dynamics in the Atmosphere) aerosol and cloud chamber of Forschungszentrum Karlsruhe can be used to test the ice forming ability of aerosols. The AIDA chamber is extensively instrumented including pressure, temperature and humidity sensors, and optical particle counters. Expansion cooling using mechanical pumps leads to ice supersaturation conditions and possible ice formation. In order to describe the evolving chamber conditions during an expansion, a parcel model was modified to account for diabatic heat and moisture interactions with the chamber walls. Model results are shown for a series of expansions where the initial chamber temperature ranged from −20°C to −60°C and which used desert dust as ice forming nuclei. During each expansion, the initial formation of ice particles was clearly observed. For the colder expansions there were two clear ice nucleation episodes. In order to test the ability of the model to represent the changing chamber conditions and to give confidence in the observations of chamber temperature and humidity, and ice particle concentration and mean size, ice particles were simply added as a function of time so as to reproduce the observations of ice crystal concentration. The time interval and chamber conditions over which ice nucleation occurs is therefore accurately known, and enables the model to be used as a test bed for different representations of ice formation.