Didier Voisin

Scavenging of acidic gases (HCOOH, CH3COOH, HNO3, HCl, and SO2) and ammonia in mixed liquid‐solid water clouds at the Puy de Dôme mountain (France)

In order to study scavenging processes of chemical species in mixed phase clouds, in-cloud field measurements were conducted in December 1997 at the Puy de Dome mountain (center of France, 1465 m above sea level). Soluble species including NH+4, Cl−;, NO3−3, SO−4, HCOO−, CH3COO−, and C2O−4 present in the different phases (supercooled water droplets, rimed snowflakes, interstitial gases, and aerosols) of cold clouds have been investigated. Conducted in parallel to microphysical studies of clouds (liquid water and ice contents, and size distribution of hydrometeors), these chemical investigations allow us to examine the partitioning of strong (HNO3 and HCl) and weak (SO2, HCOOH, and CH3COOH) acids as well as ammonia between interstitial air and the condensed phases (liquid and solid water particles) in mixed clouds present during winter at midlatitude regions. From that, we discuss the processes by which these key atmospheric species are taken up from the gas phase by the condensed phases (liquid and ice) in these cold clouds. We examine several factors which are of importance in driving the final composition of cloud ice. They include the partitioning of species between gaseous and supercooled liquid phases, the amount of rimed ice collected by snowflakes, and the retention of gas during shock freezing of supercooled droplets onto ice particles. Strong acids (HCl and HNO3) as well as NH3, being sufficiently soluble in water, are mainly partitioned into supercooled water droplets. Furthermore, being subsaturated in liquid droplets, these species are well retained in rimed ice. For these species, riming is found to be the main process driving the final composition of snowflakes, direct incorporation from the gas phase during growth of snowflakes remaining insignificant because of low concentrations in the gas phase. For light carboxylic acids the riming process mainly determines the composition of the snowflakes, but an additional significant contribution by gas incorporation during the growth of snowflakes cannot be excluded. SO2 is also present at significant levels in the interstitial air and is poorly retained in ice during riming of supercooled water droplets. However, hydroxymethanesulfonate (HMSA) was likely present in supercooled liquid droplets, making it difficult to evaluate by which mechanism S(IV) (i.e., HMSA plus SO2) has been incorporated into snowflakes.

A Model for Tropospheric Multiphase Chemistry: Application to One Cloudy Event During the CIME Experiment

In this study, we have used a multiphase box model which takes into account an explicit chemistry mechanism for both gas and aqueous phase for a rural environment and the kinetic of mass transfer between phases (Schwartz, 1986). The model is, then, initialized with multiphase measurements performed by Voisin et al. (2000) during the CIME experiment. The 13th December 1997, the cloud chemistry is mainly governed by high Nox and high formaldehyde levels and by an acidic pH in the droplets. A comparison of the model results is performed versus recent theoretical results from Herrmann et al. (1999), who proposed a slightly different chemical scheme, including C2 chemistry and transition metal chemistry but neglecting some reaction pathways, such as the one involving OHCH2O2 radical and using unrealistic microphysical cloud conditions (cloud duration, constant liquid water content, small droplet radius).

Can we model snow photochemistry? Problems with the current approaches

Snow is a very active photochemical reactor that considerably affects the composition and chemistry of the lower troposphere in polar regions. Snow photochemistry models have therefore been recently developed to describe these processes. In all those models, the chemically active medium is a brine formed at the surface of snow crystals by impurities whose presence cause surface melting. Reaction and photolysis rate coefficients are those measured in dilute liquid solutions. Here, we critically examine the basis for these models by considering the structure of ice crystal surfaces, the processes involved in the interactions between impurities and ice crystals, the location of impurities in snow, and the reactivity of impurities in the various media present in snow. We conclude that the brine formed by impurities can only be present in grooves at grain boundaries and cannot cover ice crystal surfaces because of insufficient ice wettability. It is then very likely that most reactions in snow do not take place in liquids, but rather either on an actual ice surface highly different from a liquid or in particulate matter contained in snow, such as organic particles that are thought to contain most snow chromophores. We discuss why some snow models appear to adequately reproduce some observations, concluding that they are insufficiently constrained and that the use of adjustable parameters allows acceptable fits. We discuss the complexity of developing a snow model without adjustable parameters and with a predictive value. We conclude that reaching this goal in the near future is a tremendous challenge. Modeling attempts focused on snow where the impact of organic particles is minimal, such as on the east Antarctic plateau, represents the best chance of midterm success.

The specific surface area and chemical composition of diamond dust near Barrow, Alaska

2006, when conditions were similar. The SSA of DD ranges from 79.9 to 223 m 2 kg � 1 . The calculated ice surface area in the atmosphere reaches 11000 (� 70%) mm 2 cm � 3 , much higher than the aerosol surface area. However, the impact of DD on the downwelling and upwelling light fluxes in the UV and visible is negligible. The composition of DD is markedly different from that of snow on the surface. Its concentrations in mineral ions are much lower, and its overall composition is acidic. Its concentrations in aldehydes, DOC, H2O2 and mercury are much higher than in surface snows. Our interpretation is that DOC from the oceanic surface microlayer, coming from open leads in the ice off of Barrow, is taken up by DD. Active chemistry in the atmosphere takes place on DD crystal surfaces, explaining its high concentrations in aldehydes and mercury. After deposition, active photochemistry modifies DD composition, as seen from the modifications in its absorption spectra and aldehyde and H2O2 content. This probably leads to the emissions of reactive species to the atmosphere.

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.

Sensitive determination of glyoxal, methylglyoxal and hydroxyacetaldehyde in environmental water samples by using dansylacetamidooxyamine derivatization and liquid chromatography/fluorescence

In this study we improved the dansylacetamidooxyamine (DNSAOA)-LC-fluorescence method for the determination of aqueous-phase glyoxal (GL), methylglyoxal (MG) and hydroxyacetaldehyde (HA). As derivatization of dicarbonyls can potentially lead to complex mixtures, a thorough study of the reaction patterns of GL and MG with DNSAOA was carried out. Derivatization of GL and MG was shown to follow the kinetics of successive reactions, yielding predominantly doubly derivatized compounds. We verified that the bis-DNSAOA structure of these adducts exerted only minor influence on their fluorescence properties. Contrary to observations made with formaldehyde, derivatization of GL, MG and, to a lesser extent of HA, was shown to be faster in acidic (H(2)SO(4)) medium with a maximum of efficiency for acid concentrations of ca. 2.5 mM. Concomitant separation of GL, MG, HA and of single carbonyls was achieved within 20 min by using C(18) chromatography and a gradient of CH(3)CN in water. Detection limits of 0.27, 0.17 and 0.12 nM were determined for GL, MG and HA, respectively. Consequently, low sample volumes are sufficient and, unlike numerous published methods, neither preconcentration nor large injection volumes are necessary to monitor trace-level samples. The method shows relative measurement uncertainties better than ±15% at the 95% level of confidence and good dynamic ranges (R(2)>0.99) from 0.01 to 1.5 μM for all carbonyls. GL, MG and HA were identified for the first time in polar snow samples, but also in saline frost flowers for which unexpected levels of 0.1-0.6 μM were measured. Concentrations in the 0.02-2.3 μM range were also measured in cloud water. In most samples, a predominance of HA over GL and MG was observed.

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.

Cloud Processing of Secondary Organic Aerosol from Isoprene and Methacrolein Photooxidation

Aerosol-cloud interaction contributes to the largest uncertainties in the estimation and interpretation of the Earth’s changing energy budget. The present study explores experimentally the impacts of water condensation-evaporation events, mimicking processes occurring in atmospheric clouds, on the molecular composition of secondary organic aerosol (SOA) from the photooxidation of methacrolein. A range of on- and off-line mass spectrometry techniques were used to obtain a detailed chemical characterization of SOA formed in control experiments in dry conditions, in triphasic experiments simulating gas-particle-cloud droplet interactions (starting from dry conditions and from 60% relative humidity (RH)), and in bulk aqueous-phase experiments. We observed that cloud events trigger fast SOA formation accompanied by evaporative losses. These evaporative losses decreased SOA concentration in the simulation chamber by 25–32% upon RH increase, while aqueous SOA was found to be metastable and slowly evaporated after cloud dissipation. In the simulation chamber, SOA composition measured with a high-resolution time-of-flight aerosol mass spectrometer, did not change during cloud events compared with high RH conditions (RH > 80%). In all experiments, off-line mass spectrometry techniques emphasize the critical role of 2-methylglyceric acid as a major product of isoprene chemistry, as an important contributor to the total SOA mass (15–20%) and as a key building block of oligomers found in the particulate phase. Interestingly, the comparison between the series of oligomers obtained from experiments performed under different conditions show a markedly different reactivity. In particular, long reaction times at high RH seem to create the conditions for aqueous-phase processing to occur in a more efficient manner than during two relatively short cloud events.

Atmospheric nitrate export in streams along a montane to urban gradient

Nitrogen (N) emissions associated with urbanization exacerbate the atmospheric N influx to remote ecosystems - like mountains -, leading to well-documented detrimental effects on ecosystems (e.g., soil acidification, pollution of freshwaters). Here, the importance and fate of N deposition in a watershed was evaluated along a montane to urban gradient, using a multi-isotopic tracers approach (Δ17O, δ15N, δ18O of nitrate, δ2H and δ18O of water). In this setting, the montane streams had higher proportions of atmospheric nitrate compared to urban streams, and exported more atmospheric nitrate on a yearly basis (0.35 vs 0.10 kg-Nha-1yr-1). In urban areas, nitrate exports were driven by groundwater, whereas in the catchment head nitrate exports were dominated by surface runoff. The main sources of nitrate to the montane streams were microbial nitrification and atmospheric deposition, whereas microbial nitrification and sewage leakage contributed most to urban streams. Based on the measurement of δ15N and δ18O-NO3-, biological processes such as denitrification or N assimilation were not predominant in any streams in this study. The observed low δ15N and δ18O range of terrestrial nitrate (i.e., nitrate not coming from atmospheric deposition) in surface water compared to literature suggests that atmospheric deposition may be underestimated as a direct source of N.

Tracing the fate of atmospheric nitrate in a subalpine watershed using Δ17O

Nitrogen is an essential nutrient for life on Earth, but in excess, it can lead to environmental issues (e.g., N saturation, loss of biodiversity, acidification of lakes, etc.). Understanding the nitrogen budget (i.e., inputs and outputs) is essential to evaluate the prospective decay of the ecosystem services (e.g., freshwater quality, erosion control, loss of high patrimonial-value plant species, etc.) that subalpine headwater catchments provide, especially as these ecosystems experience high atmospheric nitrogen deposition. Here, we use a multi-isotopic tracer (Δ17O, δ15N and δ18O) of nitrate in aerosols, snow, and streams to assess the fate of atmospherically deposited nitrate in the subalpine watershed of the Lautaret Pass (French Alps). We show that atmospheric N deposition contributes significantly to stream nitrate pool year-round, either by direct inputs (up to 35%) or by in situ nitrification of atmospheric ammonium (up to 35%). Snowmelt in particular leads to high exports of atmospheric nitrate, most likely fast enough to impede assimilation by surrounding ecosystems. Yet, in a context of climate change, with shorter snow seasons, and increasing nitrogen emissions, our results hint at possibly stronger ecological consequences of nitrogen atmospheric deposition in the close future.