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Single particle analysis of the accumulation mode aerosol over the northeast Amazonian tropical rain forest, Surinam, South America

Single particle analysis of aerosols particles larger than 0.2 μm diameter was performed on 24 samples collected over Surinam tropical rain forest and in the adjacent marine boundary layer (MBL) during the LBA-CLAIRE 98 campaign in March 1998. Elemental composition and morphology of 2308 particles was determined using SEM-EDX. The aerosol particles were divided into seven groups according to their chemical composition: organic particles, mineral dust, aged mineral dust, sea salt, aged sea salt, Ca-rich, and biogenic aerosol. However the organic material in aerosol particles cannot be identified directly by SEM-EDX, we present indirect method of detection of organic material using this technique. Samples were further divided with respect to the distinct atmospheric layers present in the tropical troposphere including MBL, continental mixed layer, cloud convective layer, free troposphere and region of deep convection outflow. The organic and mineral dust particles are two major groups observed over the rainforest. In the MBL also sea salt particles represented a large fraction between 15 and 27%. The organic particles control much of the chemical characteristic of the aerosol in the continental tropical troposphere. Their abundance ranged from less than 20% in the MBL to more than 90% in the free troposphere between 4.5- and 12.6-km altitude. During the transport of the air masses from the MBL over the rain forest, fraction of organic aerosol particles more than doubled, reaching 40–60% in the continental boundary layer. This increase was attributed to direct emissions of biogenic aerosols from the tropical vegetation. The high fraction of the organic accumulation mode particles in the upper tropical troposphere could be a good indicator for the air masses originated over the tropical rain forest.
Reactive and organic halogen species in three different European coastal environments

We present results of three field campaigns using active longpath DOAS (Differential Optical Absorption Spectroscopy) for the study of reactive halogen species (RHS) BrO, IO, OIO and I2. Two recent field campaigns took place in Spring 2002 in Dagebüll at the German North Sea Coast and in Spring 2003 in Lilia at the French Atlantic Coast of Brittany. In addition, data from a campaign in Mace Head, Ireland in 1998 was partly re-evaluated. During the recent field campaigns volatile halogenated organic compounds (VHOCs) were determined by a capillary gas chromatograph coupled with an electron capture detector and an inductively coupled plasma mass spectrometer (GC/ECD-ICPMS) in air and water. Due to the inhomogeneous distribution of macroalgae at the German North Sea Coast we found a clear connection between elevated levels of VHOCs and the appearance of macroalgae. Extraordinarily high concentrations of several VHOCs, especially CH3I and CH3Br of up to 1830 pptv and 875 pptv, respectively, were observed at the coast of Brittany, demonstrating the outstanding level of bioactivity there. We found CH2I2 at levels of up to 20 pptv, and a clear anti-correlation with the appearance of IO. The IO mixing ratio reached up to 7.7±0.5 ppt(pmol/mol) during the day, in reasonable agreement with model studies designed to represent the meteorological and chemical conditions in Brittany. For the two recent campaigns the DOAS spectra were evaluated for BrO, OIO and I2, but none of these species could be clearly identified (average detection limits around 2 ppt, 3 ppt, 20 ppt, resp., significantly higher in individual cases). Only in the Mace Head spectra evidence was found for the presence of OIO. Since macroalgae under oxidative stress are suggested to be a further source for I2 in the marine boundary layer, we re-analyzed spectra in the 500–600 nm range taken during the 1998 PARFORCE campaign in Mace Head, Ireland, which had not previously been analyzed for I2. We identified molecular iodine above the detection limit (~20 ppt), with peak mixing ratios of 61±12 ppt. Since I2 was undetectable during the Brittany campaign, we suggest that iodine may not be released into the atmosphere by macroalgae in general, but only by a special type of the laminaria species under oxidative stress. Only during periods of extraordinarily low water (spring-tide), the plant is exposed to ambient air and may release gaseous iodine in some way to the atmosphere. The results of our re-analysis of spectra from the PARFORCE campaign in 1998 support this theory. Hence, we feel that we can provide an explanation for the different I2 levels in Brittany and Mace Head.
Indications of thin cirrus clouds in the stratosphere at mid-latitudes

This study is devoted to the possible presence of cirrus clouds in the stratosphere. Three months of lidar data collected in the south of France (44° N) for detection of stratospheric cirrus are carefully analyzed. Most of the cirrus clouds appear to be located in the troposphere below the dynamical tropopause even when the cloud top is close to the thermal tropopause. Ten cirrus cases are found to be unambiguously located above the local dynamical tropopause according to high-resolution PV advection calculations. The highest cloud detected above the local tropopause (nearly 3 km above) is observed inside air masses that originate from the sub-tropical regions and are then transported rapidly to mid-latitudes through isentropic transport. The details of the air mass history is described with a 3-D trajectory model. The back-plumes indicate that the air mass, moist with respect to typical stratospheric air, was transported from the subtropical troposphere to the lowermost stratosphere in 4 days before detection above France. A continuous cooling of 5–10° along the trajectory took place during its transit. This cooling could have been partly responsible for the thin cirrus layer detected.
Kinetics and mechanism of the uptake of N2O5 on mineral dust at 298 K

The heterogeneous reaction of N2O5 with mineral (Saharan) dust has been studied at T=298 K using a combination of Knudsen and DRIFTS cells for kinetic and product investigations, respectively. The initial uptake coefficient has been determined to be γ=(8.0±0.3)·10−2. This uptake slowly saturates into a steady state uptake of γ=(1.3±0.3)·10−2 suggesting that reaction of N2O5 with the mineral dust surface and hydrolysis of N2O5 on the surface take place simultaneously. Both uptake coefficients have been calculated on the basis of the geometric (projected) surface area of the sample and must therefore be regarded as upper limits. In addition, the product investigations show that N2O5 is irreversibly taken up to form nitrate on the surface. Recent model calculations suggest that the uptake rates of N2O5 on Saharan dust which we measured may be large enough to influence the photo-oxidant budget of the atmosphere.
A comprehensive evaluation of water uptake on atmospherically relevant mineral surfaces: DRIFT spectroscopy, thermogravimetric analysis and aerosol growth measurements

The hygroscopicity of mineral aerosol samples has been examined by three independent methods: diffuse reflectance infrared Fourier transform spectroscopy, thermogravimetric analysis and differential mobility analysis. All three methods allow an evaluation of the water coverage of two samples, CaCO3 and Arizona Test dust, as a function of relative humidity. For the first time, a correlation between absolute gravimetric measurements and the other two (indirect) methods has been established. Water uptake isotherms were reliably determined for both solids which at 298 K and 80% relative humidity exhibited similar coverages of ~4 monolayers. However, the behaviour at low relative humidity was markedly different in the two cases, with Arizona Test Dust showing a substantially higher affinity for water in the contact layer. This is understandable in terms of the chemical composition of these two materials. The mobility analysis results are in good accord with field observations and with our own spectroscopic and gravimetric measurements. These findings are of value for an understanding of atmospheric chemical processes.
A scaling analysis of ozone photochemistry: II Investigation of the similarity relationship

The similarity relationship for maximum ozone concentration as a function of initial precursor concentrations developed in the first article of this 2-part series exhibits a scale break, most easily seen after a Weibull transformation, which identifies a characteristic scale for ozone photochemistry. In this paper, we investigate the similarity relationship using simple semi-quantitative models and model output. From this investigation, we develop a set of properties characterizing ozone-precursor relationships. We find the scaling break is associated with a change in the temporal variability of ozone production. Finally, we examine a series of smog chamber experiments for evidence of a scaling break. We find the data support a slight break after suitable transformation. It is difficult to tell if the lack of distinct break is due to smog chamber experimental limitations, a bias in the test conditions or if the processes leading to the scaling break are overly enhanced by chemical mechanisms.
On the changing seasonal cycles and trends of ozone at Mace Head, Ireland

A seasonal-trend decomposition technique based on a locally-weighted regression smoothing (Loess) approach has been used to decompose monthly ozone concentrations at Mace Head (Ireland) into trend, seasonal and irregular components. The trend component shows a steady increase from 1990–2004, which is confirmed by statistical testing which shows that ozone concentrations at Mace Head have increased at the p=0.06 level by 0.18±0.04 ppb yr−1. By considering different air mass origins using a trajectory analysis, it has been possible to separate air masses into "polluted" and "unpolluted" origins. The seasonal-trend decomposition technique confirms the different seasonal cycles of these air mass origins with unpolluted air mass maxima in April and polluted air mass maxima in July/August. A detailed consideration of the seasonal component reveals different behaviour depending on the air mass origin. For baseline unpolluted air arriving at Mace Head there has been a gradual increase in the seasonal amplitude, driven by a declining summertime component. The amplitude of the seasonal component of baseline air is controlled by a maximum in April and a minimum in July. For polluted air mass trajectories, there was a substantial reduction in the amplitude of the seasonal component from 1990–1997. However, post-1997 results indicate that the seasonal amplitude in polluted air masses arriving at Mace Head is increasing. Furthermore, there has been a shift in the months controlling the size of the seasonal amplitude in polluted air from a maximum in May and minimum in January in 1990 to a maximum in April and a minimum in July by 2001. This finding suggests that there has been a steadily decreasing influence of polluted air masses arriving from Europe. These air masses have therefore increasingly taken on the attributes of baseline air.
Kinetic study of the gas-phase reaction of atomic chlorine with a series of aldehydes

The reactions of Cl atoms with a series of unsaturated aldehydes have been investigated for the first time using a relative method. In order to obtain additional information for a qualitative structure versus reactivity discussion, we have also determined the rate coefficients for the reactions of atomic chlorine with their respective saturated aldehydes. These relative measurements were performed at room temperature and atmospheric pressure of air and N2, by using ethane, propene and 1-butene as reference compounds. The weighted average relative rate constants obtained, kCl±2σ (in units of cm3 molecule−1 s−1) were: trans-2-pentenal (1.31±0.19)×10−10; trans-2-hexenal (1.92±0.22)×10−10; trans-2-heptenal (2.40±0.29)×10−10; n-pentanal (2.56±0.27)×10−10; n-hexanal (2.88±0.37)×10−10; n-heptanal (3.00±0.34)×10−10. Finally, results and atmospheric implications are discussed and compared with the reactivity with OH and NO3 radicals.
Corrigendum to: “Real-time measurements of ammonia, acidic trace gases and water-soluble inorganic aerosol species at a rural site in the Amazon Basin" published in Atmos. Chem. Phys., 4, 967–987, 2004
The thermal and dynamical state of the atmosphere during polar mesosphere winter echoes

In January 2005, a total of 18 rockets were launched from the Andøya Rocket Range in Northern Norway (69° N) into strong VHF radar echoes called "Polar Mesosphere Winter Echoes" (PMWE). The echoes were observed in the lower and middle mesosphere during large solar proton fluxes. In general, PMWE occur much more seldom compared to their summer counterparts PMSE (typical occurrence rates at 69° N are 1–3% vs. 80%, respectively). Our in-situ measurements by falling sphere, chaff, and instrumented payloads provide detailed information about the thermal and dynamical state of the atmosphere and therefore allow an unprecedented study of the background atmosphere during PMWE. There are a number of independent observations indicating that neutral air turbulence has caused PMWE. Ion density fluctuations show a turbulence spectrum within PMWE and no fluctuations outside. Temperature lapse rates close to the adiabatic gradient are observed in the vicinity of PMWE indicating persistent turbulent mixing. The spectral broadening of radar echoes is consistent with turbulent velocity fluctuations. Turbulence also explains the mean occurrence height of PMWE (~68–75 km): viscosity increases rapidly with altitude and destroys any small scale fluctuations in the upper mesosphere, whereas electron densities are usually too low in the lower mesosphere to cause significant backscatter. The seasonal variation of echoes in the lower mesosphere is in agreement with a turbulence climatology derived from earlier sounding rocket flights. We have performed model calculations to study the radar backscatter from plasma fluctuations caused by neutral air turbulence. We find that volume reflectivities observed during PMWE are in quantitative agreement with theory. Apart from turbulence the most crucial requirement for PMWE is a sufficiently large number of electrons, for example produced by solar proton events. We have studied the sensitivity of the radar echo strength on various parameters, most important electron number density and turbulence intensity. Our observational and theoretical considerations do not provide any evidence that charged aerosol particles are needed to explain PMWE, in contrast to the summer echoes which owe their existence to charged ice particles.