K. Sellegri

Seasonal Characteristics of the Physicochemical Properties of North Atlantic Marine Atmospheric Aerosols

The aerosol size distribution modal diameters show seasonal variations, 0.031 mm in winter and 0.049 mm in summer for the Aitken mode and 0.103 mm in winter and 0.177 mm in summer for the accumulation mode. The accumulation mode mass also showed a seasonal variation, minimum in winter and maximum in summer. A supermicron sized particle mode was found at 2 mm for all seasons showing 30% higher mass concentration during winter than summer resulting from higher wind speed conditions. Chemical analysis showed that the concentration of sea salt has a seasonal pattern, minimum in summer and maximum in winter because of a dependency of sea-salt load on wind speeds. By contrast, the non-sea-salt (nss) sulphate concentration in fine mode particles exhibited lower values during winter and higher values during midsummer. The water soluble organic carbon (WSOC) and total carbon (TC) analysis also showed a distinctive seasonal pattern. The WSOC concentration during the high biological activity period peaked at 0.2 mgC m A3 , while it was lower than 0.05 mgC m A3 during the low biological activity period. The aerosol light scattering coefficient showed a minimum value of 5.5 Mm A1 in August and a maximum of 21 Mm A1 in February. This seasonal variation was due to the higher contribution of sea salt in the MBL during North Atlantic winter. By contrast, aerosols during late spring and summer exhibited larger angstrom parameters than winter, indicating a large contribution of the biogenically driven fine or accumulation modes. Seasonal characteristics of North Atlantic marine aerosols suggest an important link between marine aerosols and biological activity through primary production of marine aerosols.

High frequency new particle formation in the Himalayas

Rising air pollution levels in South Asia will have worldwide environmental consequences. Transport of pollutants from the densely populated regions of India, Pakistan, China, and Nepal to the Himalayas may lead to substantial radiative forcing in South Asia with potential effects on the monsoon circulation and, hence, on regional climate and hydrological cycles, as well as to dramatic impacts on glacier retreat. An improved description of particulate sources is needed to constrain the simulation of future regional climate changes. Here, the first evidence of very frequent new particle formation events occurring up to high altitudes is presented. A 16-month record of aerosol size distribution from the Nepal Climate Observatory at Pyramid (Nepal, 5,079 m above sea level), the highest atmospheric research station, is shown. Aerosol concentrations are driven by intense ultrafine particle events occurring on >35% of the days at the interface between clean tropospheric air and the more polluted air rising from the valleys. During a pilot study, we observed a significant increase of ion cluster concentrations with the onset of new particle formation events. The ion clusters rapidly grew to a 10-nm size within a few hours, confirming, thus, that in situ nucleation takes place up to high altitudes. The initiation of the new particle events coincides with the shift from free tropospheric downslope winds to thermal upslope winds from the valley in the morning hours. The new particle formation events represent a very significant additional source of particles possibly injected into the free troposphere by thermal winds.

Surfactants and submicron sea spray generation

Laboratory experiments have been carried out to elucidate the role of surfactants on the primary marine aerosol production of submicron marine aerosols. A synthetic surfactant SDS was used in conjunction with artificially generated seawater, and the resultant bubble-mediated aerosol produced was observed. At 23°C, the aerosol distribution resulting from the use of surfactant-free seawater comprised three modes: (1) a dominant accumulation mode at 110 nm; (2) an Aitken mode at 45 nm; and (3) a third mode, at 300 nm, resulting from forced bursting of bubbles. The forced bursting occurs when bubbles fail to burst upon reaching the surface and are later shattered by splashing associated with breaking waves and/or wind pressure at the surface. At 4°C, the accumulation mode diameter was reduced to 85 nm, the Aitken mode diameter was reduced to <30 nm and the 300 nm mode diameter was reduced to 200 nm. With the addition of SDS, the relative importance of the mode resulting from forced bursting increased dramatically. The laboratory results were compared to the observed seasonality of North Atlantic marine aerosol where a progression from mode radii minima in winter to maxima in summer is seen. The bimodality and the seasonality in modal diameter can be mostly explained by a combination of the three modes observed in the laboratory and their variation as a function of sea-surface temperature and seawater surfactant concentration. These results indicate that submicron primary aerosol modes would on a first approximation result from bubble bursting processes, although evidences of additional secondary processes leading, during summer, to a higher amplitude of the Aitken mode and mode 2 smoothed into mode 3 still need to be investigated. Copyright 2006 by the American Geophysical Union.

Quantification of Coastal New Ultra-Fine Particles Formation from In situ and Chamber Measurements during the BIOFLUX Campaign

Environmental Context. Secondary processes leading to the production of ultra-fine particles by nucle- ation are still poorly understood. A fraction of new particles formed can grow into radiatively active sizes, where they can directly scatter incoming solar radiation and, if partly water soluble, contribute to the cloud condensation nuclei population. New particle formation events have been frequently observed at the Mace Head Atmospheric Research Station (western Ireland), under low tide and sunny conditions, leading to the hypothesis that new particles are formed from iodo-species emitted from macroalgae. Abstract. New particle formation processes were studied during the BIOFLUX campaign in September 2003 and June 2004. The goals were to bring new information on the role of I2 in new particle formation from seaweeds and to quantify the amount of I2 emitted and new particles formed by a given amount of seaweed. These two goals were achieved by using a simulation chamber filled with selected species of seaweeds from the Mace Head area and flushed with particle-free atmospheric air. It was found that total particle concentrations and particles in the 3-3.4 nm size range produced in the chamber are positively correlated with gaseous I2 concentrations emitted by the seaweeds, with a typical source rate of 2800 particles cm −3 ppt −1 (I2) in the 3-3.4 nm size range. In fact, I2 and particle concentrations are also both directly positively correlated with the seaweed mass (64 300 particles cm −3 formed per kg of seaweed, and 24 ppt of I2 per kg of seaweeds) until saturation was reached for a seaweed biomass of 7.5 kg m −2 . From the chamber experiments, the flux of 3-3.4 nm particles was calculated to be 2.5 × 10 10 m −2 s −1 for a seaweed loading of 2.5 kg m −2 (representative of a typical seaweed field density), decreasing to 1 × 10 10 m −2 s −1 for a seaweed loading of 1 kg m −2 . At a seaweed loading of 2.5 kg m −2 , the growth rate of particles produced in the chamber was calculated to be 1.2 nm min −1 . The source rates and growth rates determined from the chamber experiments were used in conjunction with seaweed coverage in and around Mace Head to produce local emission inventories for a meso-scale dispersion model. Comparison of the resulting aerosol size distributions from the model simulations and those observed exhibited good agreement suggesting that the chamber fluxes and growth rates are consistent with those associated with the tidal emission areas in and around Mace Head.

Chemical composition of marine aerosol in a Mediterranean coastal zone during the FETCH experiment

The chemical composition of marine aerosols was studied during the Flux, Etats de la mer, Teledetection en Conditions de fetch variable (FETCH) experiment that took place in the northwestern Mediterranean Sea in March/April 1998. Coastal marine aerosols were collected using a 13-stage low-pressure impactor and analyzed by ion chromatography. Samples were characterized according to their continental or marine origin in order to better understand the processes affecting the chemical composition of particles during advection over a coastal zone. Strong anthropogenic influence was observed up to 100 km from the coast illustrated by (1) NH4/nss-SO4 association with ratios ranging from 0.9 to 2.1, and for some cases NH4/nss-SO4-NO3 bicorrelation; (2) chloride depletion associated with supermicron NO3, indicating previous reaction between nitric acid and NaCl; and (3) elevated NO3 fraction in the submicron range when the air mass was rain-washed. New particle formation was not detected during the campaign from either bubble bursting or from dimethylsulfide oxidation products. Nss sulfate and methanesulfonic acid appear to condense on the numerous preexisting particles rather than undergoing gas-to-particle conversion. Formation of sea-salt supermicron aerosol takes place rapidly to represent 80% of the total ionic species as little as 25 km from the coast.

Comparative trends and seasonal variation of 7Be, 210Pb and 137Cs at two altitude sites in the central part of France

The atmospheric concentrations of ¹³⁷Cs, ²¹⁰Pb, and ⁷Be were measured over a three-year period at two research stations located less than 12 km apart and at different altitudes (puy de Dôme, 1465 m a.s.l. and Opme, 660 m a.s.l., France). Seasonal trends in all radionuclides were observed at both stations, with high concentration measured during the summer and low concentrations during the winter. The ²¹⁰Pb concentrations at both stations were similar to each other. Higher concentrations of both ⁷Be and ¹³⁷Cs were measured at puy de Dôme than at Opme. These observations can be explained by the stratospheric and upper tropospheric sources of ⁷Be and the long-range transportation of ¹³⁷Cs at high altitudes. Air mass origins during sampling periods were classified into several groups by their route to the stations (marine, marine modified, continental and mediterranean). We observed that ⁷Be concentrations were constant regardless of the air mass origins, unlike ¹³⁷Cs and ²¹⁰Pb concentrations that increased when influenced by continental air masses. Higher ⁷Be concentrations were observed when air masses were arriving from the upper troposphere than from the boundary layer, the opposite was observed for ¹³⁷Cs. The temporal trend in concentrations of ⁷Be shows good agreement with previous modelling studies suggesting that there is a good understanding of its sources and the atmospheric vertical mixing of this radionuclide. The sources and mixing of ²¹⁰Pb, however, seem to be more complex than it appeared to be in previous modelling studies.

Ubiquity of organic nitrates from nighttime chemistry in the European submicron aerosol

In the atmosphere night time removal of volatile organic compounds (VOC) is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model (CTM) indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

Modelling Iodine Particle Formation and Growth from Seaweed in a Chamber

A sectional atmospheric chemistry and aerosol dynamics box model (AEROFOR) was further devel- oped and used to simulate ultra-fine particle formation and growth from seaweed in a chamber flushed with particle-free atmospheric air. In the model, thermodynamically stable clusters were formed by dimer nucleation of OIO vapour, whose precursor was assumed to be molecular I2 emitted by seaweed. Fractal geometry of particles was taken into account. For the I2 fluxes of (0.5-1.5) × 10 9 cm −3 s −1 the model predicted strong particle bursts, the steady state concentrations of I2 vapour and particles larger than 3 nm were as high as 4 × 10 9 −1.2 × 10 10 cm −3 and 5.0 × 10 6 -9.2 × 10 6 cm −3 respectively. The steady state was reached in less than 150 s and the predicted growth rates of 3-6 nm particles varied in the range of 1.2-3.6 nm min −1 . Sensitivity of the size distribution against I2O3 cluster formation, an extra condensable vapour, the photolysis rate of the OIO vapour as well as against the density of (OIO)n-clusters was discussed. The modelled results were in good agreement with the chamber measurements performed during the BIOFLUX campaign in September, 2003, in Mace Head, Ireland, confirming that I2 emissions and nucleation of iodine oxides can largely explain the coastal nucleation phenomenon.

Observations of nucleation of new particles in a volcanic plume

Volcanic eruptions caused major weather and climatic changes on timescales ranging from hours to centuries in the past. Volcanic particles are injected in the atmosphere both as primary particles rapidly deposited due to their large sizes on time scales of minutes to a few weeks in the troposphere, and secondary particles mainly derived from the oxidation of sulfur dioxide. These particles are responsible for the atmospheric cooling observed at both regional and global scales following large volcanic eruptions. However, large condensational sinks due to preexisting particles within the plume, and unknown nucleation mechanisms under these circumstances make the assumption of new secondary particle formation still uncertain because the phenomenon has never been observed in a volcanic plume. In this work, we report the first observation of nucleation and new secondary particle formation events in a volcanic plume. These measurements were performed at the puy de Dôme atmospheric research station in central France during the Eyjafjallajokull volcano eruption in Spring 2010. We show that the nucleation is indeed linked to exceptionally high concentrations of sulfuric acid and present an unusual high particle formation rate. In addition we demonstrate that the binary H2SO4 - H2O nucleation scheme, as it is usually considered in modeling studies, underestimates by 7 to 8 orders of magnitude the observed particle formation rate and, therefore, should not be applied in tropospheric conditions. These results may help to revisit all past simulations of the impact of volcanic eruptions on climate.

Evidence of atmospheric nanoparticle formation from emissions of marine microorganisms

Earth, as a whole, can be considered as a living organism emitting gases and particles into its atmosphere, in order to regulate its own temperature. In particular, oceans may respond to climate change by emitting particles that ultimately will influence cloud coverage. At the global scale, a large fraction of the aerosol number concentration is formed by nucleation of gas-phase species, but this process has never been directly observed above oceans. Here we present, using semicontrolled seawater-air enclosures, evidence that nucleation may occur from marine biological emissions in the atmosphere of the open ocean. We identify iodine-containing species as major precursors for new particle clusters’ formation, while questioning the role of the commonly accepted dimethyl sulfide oxidation products, in forming new particle clusters in the region investigated and within a time scale on the order of an hour. We further show that amines would sustain the new particle formation process by growing the new clusters to larger sizes. Our results suggest that iodine-containing species and amines are correlated to different biological tracers. These observations, if generalized, would call for a substantial change of modeling approaches of the sea-to-air interactions.