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A new parametrization for ambient particle formation over coniferous forests and its potential implications for the future

Atmospheric new particle formation is a general phenomenon observed over coniferous forests. So far nucleation is either parameterised as a function of gaseous sulphuric acid concentration only, which is unable to explain the observed seasonality of nucleation events at different measurement sites, or as a function of sulphuric acid and organic molecules. Here we introduce different nucleation parameters based on the interaction of sulphuric acid and terpene oxidation products and elucidate the individual importance. They include basic trace gas and meteorological measurements such as ozone and water vapour concentrations, temperature (for terpene emission) and UV B radiation as a proxy for OH radical formation. We apply these new parameters to field studies conducted at conducted at Finnish and German measurement sites and compare these to nucleation observations on a daily and annual scale. General agreement was found, although the specific compounds responsible for the nucleation process remain speculative. This can be interpreted as follows: During cooler seasons the emission of biogenic terpenes and the OH availability limits the new particle formation while towards warmer seasons the ratio of ozone and water vapour concentration seems to dominate the general behaviour. Therefore, organics seem to support ambient nucleation besides sulphuric acid or an OH-related compound. Using these nucleation parameters to extrapolate the current conditions to prognosed future concentrations of ozone, water vapour and organic concentrations leads to a significant potential increase in the nucleation event number.
Bimodal variation in mercury wet deposition to the coastal zone of the southern Baltic

In the following periods: November 2005–June 2006 and October 2007–January 2009, concentrations and deposition rates of total mercury (THg) and Hg(II) were measured in precipitation over the urbanized and industrialized area of the southern Baltic – the city of Gdynia. Rains over the coastal zone had different concentrations of total mercury, they ranged from 8.6 to 118.0 ng L−1, out of which about 32% were labile, inorganic forms, easily reducible in a SnCl2 solution. Over the southern Baltic two maxima of concentrations were observed: first, in the heating season and second, in the non-heating season. Elevated concentrations of mercury in precipitations during heating seasons were the result of the activity of local emission sources (intensive combustion of fossil fuels in domestic furnaces and individual power and heat generating plants). During the warm season, precipitation over the southern Baltic could clean the air from Hg reemitted from sea and land surfaces. Precipitations, which purified marine and continental air masses were responsible for the comparable input of mercury to the coastal zone. The wet deposition value in 2008 was estimated to be 28.9 μg m−2. In the coastal zone of the southern Baltic, acid precipitations with the elevated Hg concentrations are very frequent.
The representation of dust transport and missing urban sources as major issues for the simulation of PM episodes in a Mediterranean area

Due to its adverse effects on human health, atmospheric particulate matter (PM) constitutes a growing challenge for air quality management. It is also a complex subject of study. The understanding of its atmospheric evolution is indeed made difficult by the wide number of sources and the numerous processes that govern its evolution in the troposphere. As a consequence, the representation of particulate matter in chemistry-transport models needs to be permanently evaluated and enhanced in order to refine our comprehension of PM pollution events and to propose consistent environmental policies. The study presented here focuses on two successive summer particulate pollution episodes that occurred on the French Mediterranean coast. We identify and analyze the constitutive elements of the first and more massive episode and we discuss their representation within a eulerian model. The results show that the model fails in reproducing the variability and the amplitude of dust import from western Africa, and that it constitutes a strong bias in PM daily forecasts. We then focus on the lack of diurnal variability in the model, which is attributed to missing urban sources in standard emission inventories, and notably the resuspension of particles by urban road traffic. Through a sensitivity study based on PM and NOx measurements, we assess the sensitivity of PM to local emissions and the need to reconsider road traffic PM sources. In parallel, by coupling the CHIMERE-DUST model outputs to our simulation, we show that the representation of transcontinental dust transport allows a much better representation of atmospheric particles in southern France, and that it is needed in the frame of air quality management for the quantification of the anthropogenic part of particulate matter pollution.
Corrigendum to 'Peroxy radical observations over West Africa during AMMA 2006: photochemical activity in the outflow of convective systems" published in Atmos. Chem. Phys., 9, 3681–3695, 2009
New particle formation from the oxidation of direct emissions of pine seedlings

Measurements of particle formation following the gas phase oxidation of volatile organic compounds (VOCs) emitted by Scots pine (Pinus sylvestris L.) seedlings are reported. Particle formation and condensational growth both from ozone (O3) and hydroxyl radical (OH) initiated oxidation of pine emissions (about 20-120 ppb) were investigated in a smog chamber. During experiments, tetramethylethylene (TME) and 2-butanol were added to control the concentrations of O3 and OH. Particle formation and condensational growth rates were interpreted with a chemical kinetic model. Scots pine emissions mainly included α-pinene, β-pinene, Δ3-carene, limonene, myrcene and β-phellandrene, composing more than 95% of total emissions. Modeled OH concentrations in the O3- and OH-induced experiments were on the order of ~106 molecules cm−3. Our results demonstrate that OH-initiated oxidation of VOCs plays an important role in the nucleation process during the initial new particle formation stage. The highest average particle formation rate of 360 cm−3 s−1 was observed for the OH-dominated nucleation events and the lowest formation rate of less than 0.5 cm−3 s−1 was observed for the case with only O3 present as an oxidant. In contrast to the particle formation process, ozonolysis of monoterpenes appears to be much more efficient to the aerosol growth process following nucleation. Higher contributions of more oxygenated products to the SOA mass loadings from OH-dominated oxidation systems were found as compared to the ozonolysis systems. Comparison of mass and volume distributions from the aerosol mass spectrometer and differential mobility analyzer yields estimated SOA effective densities of 1.34±0.06 g cm−3 for the OH+O3 oxidation systems and 1.38±0.03 g cm−3 for the O3 dominated chemistry.
Evaluation of tropospheric ozone columns derived from assimilated GOME ozone profile observations

Tropospheric O3 column estimates are produced and evaluated from spaceborne O3 observations by the subtraction of assimilated O3 profile observations from total column observations, the so-called Tropospheric O3 ReAnalysis or TORA method. Here we apply the TORA method to six years (1996–2001) of ERS-2 GOME/TOMS total O3 and ERS-2 GOME O3 profile observations using the TM5 global chemistry-transport model with a linearized O3 photochemistry parameterization scheme. Free running TM5 simulations show good agreement with O3 sonde observations in the upper-tropospheric and lower stratospheric region (UTLS), both for short day-to-day variability as well as for monthly means. The assimilation of GOME O3 profile observations counteracts the mid-latitude stratospheric O3 drift caused by the overstrong stratospheric meridional circulation in TM5. Assimilation of GOME O3 profile observations also improves the bias and correlations in the tropical UTLS region but slightly degrades the model-to-sonde correlations and bias of extra-tropical UTLS. We suggest that this degradation is related to the large ground pixel size of the GOME O3 measurements (960×100 km) in combination with retrieval and calibration errors. The added value of the assimilation of GOME O3 profiles compared to stand-alone model simulations lays in the long term variations of stratospheric O3, not in short term synoptic variations. The evaluation of daily and monthly tropospheric O3 columns obtained from total column observations and using the TORA methodology shows that the use of GOME UV-VIS nadir O3 profiles in combination with the spatial resolution of the model does not result in satisfactory residual tropospheric ozone columns.
Airborne measurements of the nitric acid partitioning in persistent contrails

This study reports the first systematic measurements of nitric acid (HNO3) uptake in contrail ice particles at typical aircraft cruise altitudes. During the CIRRUS-III campaign cirrus clouds and almost 40 persistent contrails were probed with in situ instruments over Germany and Northern Europe in November 2006. Besides reactive nitrogen, water vapor, cloud ice water content, ice particle size distributions, and condensation nuclei were measured during 6 flights. Contrails with ages up to 12 h were detected at altitudes 10–11.5 km and temperatures 211–220 K. These contrails had a larger ice phase fraction of total nitric acid (HNO3ice/HNO3tot = 6%) than the ambient cirrus layers (3%). On average, the contrails contained twice as much HNO3ice as the cirrus clouds, 14 pmol/mol and 6 pmol/mol, respectively. Young contrails with ages below 1 h had a mean HNO3ice of 21 pmol/mol. The contrails had higher nitric acid to water molar ratios in ice and slightly higher ice water contents than the cirrus clouds under similar meteorological conditions. The differences in ice phase fractions and molar ratios between developing contrails and cirrus are likely caused by high plume concentrations of HNO3 prior to contrail formation. The location of the measurements in the upper region of frontal cirrus layers might account for slight differences in the ice water content between contrails and adjacent cirrus clouds. The observed dependence of molar ratios as a function of the mean ice particle diameter suggests that ice-bound HNO3 concentrations are controlled by uptake of exhaust HNO3 in the freezing plume aerosols in young contrails and subsequent trapping of ambient HNO3 in growing ice particles in older (age > 1 h) contrails.
Daytime SABER/TIMED observations of water vapor in the mesosphere: retrieval approach and first results

This paper describes a methodology for water vapor retrieval in the mesosphere-lower thermosphere (MLT) using 6.6 μm daytime broadband emissions measured by SABER, the limb scanning infrared radiometer on board the TIMED satellite. Particular attention is given to accounting for the non-local thermodynamic equilibrium (non-LTE) nature of the H2O 6.6 μm emission in the MLT. The non-LTE H2O(ν2) vibrational level populations responsible for this emission depend on energy exchange processes within the H2O vibrational system as well as on interactions with vibrationally excited states of the O2, N2, and CO2 molecules. The rate coefficients of these processes are known with large uncertainties that undermines the reliability of the H2O retrieval procedure. We developed a methodology of finding the optimal set of rate coefficients using the nearly coincidental solar occultation H2O density measurements by the ACE-FTS satellite and relying on the better signal-to-noise ratio of SABER daytime 6.6 μm measurements. From this comparison we derived an update to the rate coefficients of the three most important processes that affect the H2O(ν2) populations in the MLT: a) the vibrational-vibrational (V–V) exchange between the H2O and O2 molecules; b) the vibrational-translational (V–T) process of the O2(1) level quenching by collisions with atomic oxygen, and c) the V–T process of the H2O(010) level quenching by collisions with N2, O2, and O. Using the advantages of the daytime retrievals in the MLT, which are more stable and less susceptible to uncertainties of the radiance coming from below, we demonstrate that applying the updated H2O non-LTE model to the SABER daytime radiances makes the retrieved H2O vertical profiles in 50–85 km region consistent with climatological data and model predictions. The H2O retrieval uncertainties in this approach are about 10% at and below 70 km, 20% at 80 km, and 30% at 85 km altitude.
Retrieval of water vapor profile in the mesosphere from satellite ozone and hydroxyl measurements by the basic dynamic model of mesospheric photochemical system

We propose an indirect method for retrieving a number of significant minor gas constituents of the atmosphere. The technique is based on the use of so-called basic dynamic models of atmospheric photochemical systems simplified mathematically correctly in a special manner. It is applied to a mesospheric system describing day evolution of key minor gas constituents at these heights. We take as initial data experimental data of the CRISTA-MAHRSI satellite campaign of August 1997 during which ozone and hydroxyl (O3 and OH) concentrations were measured simultaneously. It is demonstrated that the use of the basic dynamic model allows retrieval of vertical distribution (within the 53–85 km range of heights) of water vapor concentration that is one of the control parameters of the mesospheric photochemistry.
Testing aerosol properties in MODIS Collection 4 and 5 using airborne sunphotometer observations in INTEX-B/MILAGRO

The 14-channel Ames Airborne Tracking Sunphotometer (AATS) was operated on a Jetstream 31 (J31) aircraft in March 2006 during MILAGRO/INTEX-B (Megacity Initiative-Local And Global Research Observations/Phase B of the Intercontinental Chemical Transport Experiment). We compare AATS retrievals of spectral aerosol optical depth (AOD) and related aerosol properties with corresponding spatially coincident and temporally near-coincident measurements acquired by the MODIS-Aqua and MODIS-Terra satellite sensors. These comparisons are carried out for the older MODIS Collection 4 (C4) and the new Collection 5 (C5) data set, the latter representing a reprocessing of the entire MODIS data set completed during 2006 with updated calibration and aerosol retrieval algorithm. Our analysis yields a direct, validated assessment of the differences between select MODIS C4 and C5 aerosol retrievals. Our analyses of 37 coincident observations by AATS and MODIS-Terra and 18 coincident observations between AATS and MODIS-Aqua indicate notable differences between MODIS C4 and C5 and between the two sensors. For MODIS-Terra, we find an average increase in AOD of 0.02 at 553 nm and 0.01 or less at the shortwave infrared (SWIR) wavelengths. The change from C4 to C5 results in less good agreement with the AATS derived spectral AOD, with average differences at 553 nm increasing from 0.03 to 0.05. For MODIS-Aqua, we find an average increase in AOD of 0.008 at 553 nm, but an increase of nearly 0.02 at the SWIR wavelengths. The change from C4 to C5 results in slightly less good agreement to the AATS derived visible AOD, with average differences at 553 nm increasing from 0.03 to 0.04. However, at SWIR wavelengths, the changes from C4 to C5 result in improved agreement between MODIS-Aqua and AATS, with the average differences at 2119 nm decreasing from −0.02 to −0.003. Comparing the Angstrom exponents calculated from AOD at 553nm and 855nm, we find an increased rms difference from AATS derived Angstrom exponents in going from C4 to C5 for MODIS-Terra, and a decrease in rms difference, hence an improvement, for the transition from C4 to C5 in MODIS-Aqua. Combining the AATS retrievals with in situ measurements of size-dependent aerosol extinction, we derive a suborbital measure of the aerosol submicron fraction (SMF) of AOD and compare it to MODIS retrievals of aerosol fine mode fraction (FMF). Our analysis shows a significant rms-difference between the MODIS-Terra FMF and suborbitally-derived SMF of 0.17 for both C4 and C5. For MODIS-Aqua, there is a slight improvement in the transition from C4 to C5, with the rms-difference from AATS dropping from 0.23 to 0.16. The differences in MODIS C4 and C5 AOD in this limited data set can be traced to changes in the reflectances input to the aerosol retrievals. An extension of the C4-C5 comparisons from the area along the J31 flight track to a larger study region between 18–23° N and 93–100° W on each of the J31 flight days supports the finding of significant differences between MODIS C4 and C5.