Jean-Luc Jaffrezo

Levoglucosan as a specific marker of fire events in Greenland snow

ABSTRACT We demonstrate the use of levoglucosan (1,6-anhydro-β-d-glucopyranose) as a source-specific proxy of past fire activity in snow pits and ice cores. Levoglucosan is unambiguously a degradation product derived from cellulose burning at temperatures greater than 300 °C and is widely used as a biomass burning marker in aerosol analyses. We analyse samples collected from a 3 m snow pit at Summit, Greenland (72°20′N, 38°45′W; 3270 m a.s.l.), with a known depositional history where biomass burning aerosols were traced from their source in a Canadian smoke plume, through their eastward transport and deposition on the Greenland ice sheet, and their eventual burial by accumulating snow layers. The snow pit levoglucosan profile replicates oxalate concentrations from a known forest fire event, suggesting the applicability of levoglucosan as a marker of past fire activity in snow and by extension in ice cores. However, levoglucosan concentration peaks in the snow pit differ from those of ammonium and potassium, which are traditionally used as biomass burning proxies in snow and ice studies but which incorporate sources other than fire activity. The source specificity of levoglucosan can help determine the past relative contribution of biomass burning aerosols when used in conjunction with other proxies in snow and ice.

The dynamic surface tension of atmospheric aerosol surfactants reveals new aspects of cloud activation

The activation of aerosol particles into cloud droplets in the Earth’s atmosphere is both a key process for the climate budget and a main source of uncertainty. Its investigation is facing major experimental challenges, as no technique can measure the main driving parameters, the Raoult’s term and surface tension, σ, for sub-micron atmospheric particles. In addition, the surfactant fraction of atmospheric aerosols could not be isolated until recently. Here we present the first dynamic investigation of the total surfactant fraction of atmospheric aerosols, evidencing adsorption barriers that limit their gradient (partitioning) in particles and should enhance their cloud-forming efficiency compared with current models. The results also show that the equilibration time of surfactants in sub-micron atmospheric particles should be beyond the detection of most on-line instruments. Such instrumental and theoretical shortcomings would be consistent with atmospheric and laboratory observations and could have limited the understanding of cloud activation until now.

Seasonal variations in heavy metals concentrations in present day Greenland snow

Thirty six snow samples collected from a 1.6 m snow pit in central Greenland, have been analysed for Pb, Cd, Zn, Cu and other species using ultraclean analytical procedures. They cover continuously a 2 year time period from summer 1992 to spring 1990, with sub-seasonal resolution. Pronounced seasonal variations of the concentrations are observed for all four heavy metals, with low values in winter, and much higher concentrations not only in spring but also in summer. The factors of variations are 75 for Pb, 31 for Cd, 22 for Zn and 48 for Cu. Estimates of the contributions from natural sources show that anthropogenic contributions are dominant for Pb, Cd and Zn while a significant fraction of Cu derives from rock and soil dust in part of the samples. Our data confirm that the high altitude central areas of the Greenland ice sheet remain isolated from the highly polluted air masses of the Arctic basin in winter. The enhanced concentrations observed in the summer layers are attributed to inputs from pin point sources in high latitude continental areas.

Seasonal variations in the origin of lead in snow at Dye 3, Greenland

Abstract The isotopic composition and concentration of lead has been measured in fresh and slightly aged snow collected at Dye 3 in southern Greenland during one full year. The lead concentration displayed large variations ranging from 14–3016 pg/g in April (spring) to 3–6 pg/g in September (summer) while the isotopic ratios changed in regular manner during the year. The 206 Pb/ 207 Pb ratios were ∼1.15 from spring to mid-summer snow, and increased in late summer to early autumn, reaching ∼1.20 in winter. These isotopic data indicate that the lead in the autumn to winter snow originated in North America, while that in spring to mid-summer snow is from Eurasia.

Oxidation of atmospheric humic like substances by ozone: a kinetic and structural analysis approach.

This work explores the heterogeneous reaction between HUmic-LIke Substances (so-called HULIS) and ozone. Genuine atmospheric HULIS were extracted from aerosol samples collected in Chamonix (France) in winter and used in coated flow tube experiments to evaluate heterogeneous uptake of O₃ on such mixtures. The uptake coefficient (γ) was investigated as a function of pH (from 2.5 to 10), O₃ concentration (from 8 to 33 × 10¹¹ molecules cm⁻³), relative humidity (20 to 65%) and photon flux (from 0 to 1.66 × 10¹⁵ photons cm⁻² s⁻¹). Reactive uptake was found to increase in the irradiated experiment with pH, humidity and photon flux. The extract was characterized before and after exposure to O₃ and/or UV light in the attempt to elucidate the effect of the photochemical aging. Carbon content measurements, UV-vis spectroscopy and functional groups analysis revealed a decrease of the UV absorbance as well as of the carbon mass content, while the functionalization rate (COOH and C═O) and therefore the polarity increased during the simulated photochemical exposure.

Source apportionment of PM10, organic carbon and elemental carbon at Swiss sites: An intercomparison of different approaches

In this study, the results of source apportionment of particulate matter (PM10), organic carbon (OC), and elemental carbon (EC) - as obtained through different approaches at different types of sites (urban background, urban roadside, and two rural sites in Switzerland) - are compared. The methods included in this intercomparison are positive matrix factorisation modelling (PMF, applied to chemical composition data including trace elements, inorganic ions, OC, and EC), molecular marker chemical mass balance modelling (MM-CMB), and the aethalometer model (AeM). At all sites, the agreement of the obtained source contributions was reasonable for OC, EC, and PM10. Based on an annual average, and at most of the considered sites, secondary organic carbon (SOC) is the component with the largest contribution to total OC; the most important primary source of OC is wood combustion, followed by road traffic. Secondary aerosols predominate in PM10. All considered techniques identified road traffic as the dominant source of EC, while wood combustion emissions are of minor importance for this constituent. The intercomparison of different source apportionment approaches is helpful to identify the strengths and the weaknesses of the different methods. Application of PMF has limitations when source emissions have a strong temporal correlation, or when meteorology has a strong impact on PM variability. In these cases, the use of PMF can result in mixed source profiles and consequently in the under- or overestimation of the real-world sources. The application of CMB models can be hampered by the unavailability of source profiles and the non-representativeness of the available profiles for local source emissions. This study also underlines that chemical transformations of molecular markers in the atmosphere can lead to the underestimation of contributions from primary sources, in particular during the summer period or when emission sources are far away from the receptor sites.

Temporal and spatial variability of snow accumulation in central Greenland

Snow accumulation records from central Greenland are explored to improve the understanding of the accumulation signal in Greenland ice core records. Results from a “forest” of 100 bamboo poles and automated accumulation monitors in the vicinity of Summit as well as shallow cores collected in the Summit and Crete areas are presented. Based on these accumulation data, a regression has been calculated to quantify the signal-to-noise variance ratio of ice core accumulation signals on a variety of temporal (1 week to 2 years) and spatial (20 m to 200 km) scales. Results are consistent with data obtained from year-round automated accumulation measurements deployed at Summit which suggest that it is impossible to obtain regional snow accumulation data with seasonal resolution using four accumulation monitors positioned over a length scale of ∼30 km. Given this understanding of the temporal and spatial dependence of noise in the ice core accumulation signal, the accumulation records from 17 shallow cores are revisited. Each core spans the time period from 1964 to 1983. By combining the accumulation records, the regional snow accumulation record has been obtained for this period. The results show that 9 of the 20 years can be identified as having an accumulation different from the 20 year mean with 99% confidence. The signal-to-noise variance ratio for the average accumulation signal sampled at annual intervals is 5.8±0.5. The averaged accumulation time series may be useful to climate modelers attempting to validate their models with accurate regional hydrologic data sets.

Current Status of Atmospheric Studies at Summit (Greenland) and Implications for Future Research

The present paper is an overview of the some of the basic questions raised by the recent experiments in Greenland, in the field of air-snow transfer of gases and particles. After an introduction that presents the frame of the ATM programme, we successively present results of studies concerning the transport of chemical species from source regions to the atmosphere of the Greenland Ice Sheet, their deposition processes, and the post deposition effects that can modify the chemical signal recorded in the snow layers. It shows that a comprehensive approach of all of these questions calls for complementary investigations in research areas covering several scales of space and time, from large scale meteorology to microscale physics. In many cases, the field studies performed during DGASP and ATM Increased significantly our knowledge of the processes involved in the transfer of chemical species from source regions to the deep ice, and allowed for the determination of the most important parameters controlling these processes. But many areas are still poorly understood, that we try to point out.

The unexpected role of bioaerosols in the Oxidative Potential of PM

AbstractBioaerosols represent up to 15–25% of PM by mass, but there is currently no assessment of their impact on Oxidative Potential (OP), or capacity of particulate matter (PM) to produce damaging oxidative reactions in the human lungs. Here, the OP of selected bioaerosols (bacteria cells vs fungal spores) was assessed through the cell-free DTT assay. Results show that bioaerosols induce Reactive Oxygen Species (ROS) production, varying along the microorganism type, species, and concentration. Fungal spores show up to 10 times more ROS generation than bacterial cells. At the highest concentrations, fungal spores present as much oxidative reactivity as the most redox-active airborne chemicals (Copper, Naphtoquinone). Moreover, bioaerosols substantially influence OP of ambient PM and that of its chemical constituents: in presence of A. fumigatus spores, the OP of Cu/NQ is increased by a factor of 2 to 5, whereas, 104 and 105  S. epidermidis bacterial cells.mL−1 halves the OP of Cu/NQ. Finally, viable and gamma-rays-killed model bioaerosols present similar oxidative reactivity, suggesting a metabolism-independent cellular mechanism. These results reveal the importance of bioaerosols for PM reactivity. PM toxicity can be modified due to bioaerosols contribution or by their ability to modulate the OP of toxic chemicals present in PM.

The importance of simulated lung fluid (SLF) extractions for a more relevant evaluation of the oxidative potential of particulate matter

Particulate matter (PM) induces oxidative stress in vivo, leading to adverse health effects. Oxidative potential (OP) of PM is increasingly studied as a relevant metric for health impact (instead of PM mass concentration) as much of the ambient particle mass do not contribute to PM toxicity. Several assays have been developed to quantify PM oxidative potential and a widely used one is the acellular dithiothreitol (DTT) assay. However in such assays, particles are usually extracted with methanol or Milli-Q water which is unrepresentative of physiological conditions. For this purpose, OPDTT measurements after simulated lung fluids (SLF) extraction, in order to look at the impact of simulated lung fluid constituents, were compared to Milli-Q water extraction measurements. Our major finding is a significant decrease of the OPDTT when the artificial lysosomal fluid (ALF) solution was used. Indeed, ligand compounds are present in the SLF solutions and some induce a decrease of the OP when compared to water extraction. Our results suggest that the effect of ligands and complexation in lining fluids towards PM contaminants probably has been underestimated and should be investigated further.