Seasonal variations in aerosol particle composition at the puy-de-Dôme research station in France

Detailed investigations of the chemical and microphysical properties of atmospheric aerosol particles were performed at the puy-de-Dôme (pdD) research station (1465 m) in autumn (September and October 2008), winter (February and March 2009), and summer (June 2010) using a compact Time-of-Flight Aerosol Mass Spectrometer (cToF-AMS). Over the three campaigns, the average mass concentrations of the non-refractory submicron particles ranged from 10 μg m<sup>−3</sup> up to 27 μg m<sup>−3</sup>. Highest nitrate and ammonium mass concentrations were measured during the winter and during periods when marine modified airmasses were arriving at the site, whereas highest concentrations of organic particles were measured during the summer and during periods when continental airmasses arrived at the site. The measurements reported in this paper show that atmospheric particle composition is strongly influenced by both the season and the origin of the airmass. The total organic mass spectra were analysed using positive matrix factorisation to separate individual organic components contributing to the overall organic particle mass concentrations. These organic components include a low volatility oxygenated organic aerosol particle (LV-OOA) and a semi-volatile organic aerosol particle (SV-OOA). Correlations of the LV-OOA components with fragments of <i>m/z</i> 60 and <i>m/z</i> 73 (mass spectral markers of wood burning) during the winter campaign suggest that wintertime LV-OOA are related to aged biomass burning emissions, whereas organic aerosol particles measured during the summer are likely linked to biogenic sources. Equivalent potential temperature calculations, gas-phase, and LIDAR measurements define whether the research site is in the planetary boundary layer (PBL) or in the free troposphere (FT)/residual layer (RL). We observe that SV-OOA and nitrate particles are associated with air masses arriving from the PBL where as particle composition measured from RL/FT airmasses contain high mass fractions of sulphate and LV-OOA. This study provides unique insights into the effects of season and airmass variability on regional aerosol particles measured at an elevated site

A single-particle characterization of a mobile Versatile Aerosol Concentration Enrichment System for exposure studies

BACKGROUND: An Aerosol Time-of-Flight Mass Spectrometer (ATOFMS) was used to investigate the size and chemical composition of fine concentrated ambient particles (CAPs) in the size range 0.2–2.6 μm produced by a Versatile Aerosol Concentration Enrichment System (VACES) contained within the Mobile Ambient Particle Concentrator Exposure Laboratory (MAPCEL). The data were collected during a study of human exposure to CAPs, in Edinburgh (UK), in February-March 2004. The air flow prior to, and post, concentration in the VACES was sampled in turn into the ATOFMS, which provides simultaneous size and positive and negative mass spectral data on individual fine particles. RESULTS: The particle size distribution was unaltered by the concentrator over the size range 0.2–2.6 μm, with an average enrichment factor during this study of ~5 (after dilution of the final air stream). The mass spectra from single particles were objectively grouped into 20 clusters using the multivariate K-means algorithm and then further grouped manually, according to similarity in composition and time sequence, into 8 main clusters. The particle ensemble was dominated by pure and reacted sea salt and other coarse inorganic dusts (as a consequence of the prevailing maritime-source climatology during the study), with relatively minor contributions from carbonaceous and secondary material. Very minor variations in particle composition were noted pre- and post-particle concentration, but overall there was no evidence of any significant change in particle composition. CONCLUSION: These results confirm, via single particle analysis, the preservation of the size distribution and chemical composition of fine ambient PM in the size range 0.2–2.6 μm after passage through the VACES concentration instrumentation

Hygroscopic Behavior and Liquid-Layer Composition of Aerosol Particles Generated from Natural and Artificial Seawater

Sea-salt aerosol (SSA) particles affect the Earth\u27s radiative balance and moderate heterogeneous chemistry in the marine boundary layer. Using conventional and environmental transmission electron microscopes (ETEM), we investigated the hygroscopic growth and liquid-layer compositions of particles generated from three types of aqueous salt solutions: sodium chloride, laboratory-synthesized seawater (S-SSA particles), and natural seawater (N-SSA particles). Three levels of morphological change were observed with the ETEM as the laboratory-generated particles were exposed to increasing relative humidity (RH). The first level, onset of observable morphological changes, occurred on average at 70, 48, and 35% RH for the NaCl, S-SSA, and N-SSA particles, respectively. The second level, rounding, occurred at 74, 66, and 57% RH for NaCl, S-SSA, and N-SSA particles, respectively. The third level, complete deliquescence, occurred at 75% RH for all particles. Collected ambient SSA particles were also examined. With the exception of deliquescence, they did not exhibit the same hygroscopic characteristics as the NaCl particles. The ambient particles, however, behaved most similarly to the synthesized and natural SSA particles, although the onset of morphological change was slightly higher for the S-SSA particles. We used energy-dispersive X-ray spectrometry to study the composition of the liquid layer formed on the S-SSA and N-SSA particles. The layer was enriched in Mg, S, and O relative to the solid particle core. An important implication of these results is that MgSO4-enriched solutions on the surface of SSA particles may be the solvents of many heterogeneous reactions

Characterizing the impact of urban emissions on regional aerosol particles: airborne measurements during the MEGAPOLI experiment

The MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) experiment took place in July 2009. The aim of this campaign was to study the aging and reactions of aerosol and gas-phase emissions in the city of Paris. Three ground-based measurement sites and several mobile platforms including instrument equipped vehicles and the ATR-42 aircraft were involved. We present here the variations in particle- and gas-phase species over the city of Paris, using a combination of high-time resolution measurements aboard the ATR-42 aircraft. Particle chemical composition was measured using a compact time-of-flight aerosol mass spectrometer (C-ToF-AMS), giving detailed information on the non-refractory submicron aerosol species. The mass concentration of black carbon (BC), measured by a particle absorption soot photometer (PSAP), was used as a marker to identify the urban pollution plume boundaries. Aerosol mass concentrations and composition were affected by air-mass history, with air masses that spent longest time over land having highest fractions of organic aerosol and higher total mass concentrations. The Paris plume is mainly composed of organic aerosol (OA), BC, and nitrate aerosol, as well as high concentrations of anthropogenic gas-phase species such as toluene, benzene, and NO_x. Using BC and CO as tracers for air-mass dilution, we observe the ratio of ΔOA / ΔBC and ΔOA / ΔCO increase with increasing photochemical age (−log(NO_x / NO_y)). Plotting the equivalent ratios of different organic aerosol species (LV-OOA, SV-OOA, and HOA) illustrate that the increase in OA is a result of secondary organic aerosol (SOA) formation. Within Paris the changes in the ΔOA / ΔCO are similar to those observed during other studies in London, Mexico City, and in New England, USA. Using the measured SOA volatile organic compounds (VOCs) species together with organic aerosol formation yields, we were able to predict ~50% of the measured organics. These airborne measurements during the MEGAPOLI experiment show that urban emissions contribute to the formation of OA and have an impact on aerosol composition on a regional scale

Nitrogen and sulphur management: challenges for organic sources in temperate agricultural systems

A current global trend towards intensification or specialization of agricultural enterprises has been accompanied by increasing public awareness of associated environmental consequences. Air and water pollution from losses of nutrients, such as nitrogen (N) and sulphur (S), are a major concern. Governments have initiated extensive regulatory frameworks, including various land use policies, in an attempt to control or reduce the losses. This paper presents an overview of critical input and loss processes affecting N and S for temperate climates, and provides some background to the discussion in subsequent papers evaluating specific farming systems. Management effects on potential gaseous and leaching losses, the lack of synchrony between supply of nutrients and plant demand, and options for optimizing the efficiency of N and S use are reviewed. Integration of inorganic and organic fertilizer inputs and the equitable re-distribution of nutrients from manure are discussed. The paper concludes by highlighting a need for innovative research that is also targeted to practical approaches for reducing N and S losses, and improving the overall synchrony between supply and demand

Major contribution of neutral clusters to new particle formation at the interface between the boundary layer and the free troposphere

The formation of new aerosol particles in the atmosphere is a key process influencing the aerosol number concentration as well as the climate, in particular at high altitude, where the newly formed particles directly influence cloud formation. However, free tropospheric new particle formation (NPF) is poorly documented due to logistic limitations and complex atmospheric dynamics around high-altitude stations that make the observation of this day-time process challenging. Recent improvements in measurement techniques make now possible the detection of neutral clusters down to similar to 1 nm sizes, which opens new horizons in our understanding of the nucleation process. Indeed, only the charged fraction of clusters has been reported in the upper troposphere up to now. Here we report day-time concentrations of charged and neutral clusters (1 to 2.5 nm mobility diameter) recorded at the interface between the boundary layer (BL) and the FT as well as in the FT at the altitude site of Puy de Dome (1465 m a.s.l.), central France, between 10 and 29 February 2012. Our findings demonstrate that in the FT, and especially at the interface between the BL and the FT, the formation of 1.5 nm neutral clusters significantly exceeds the one of ionic clusters during NPF events, clearly indicating that they dominate in the nucleation process. We also observe that the total cluster concentration significantly increases during NPF events compared to the other days, which was not clearly observed for the charged cluster population in the past. During the studied period, the nucleation process does not seem to be sulfuric acid-limited and could be promoted by the transport of pollutants to the upper troposphere, coupled with low temperatures.Peer reviewe

Using PCR-Based Detection and Genotyping to Trace Streptococcus salivarius Meningitis Outbreak Strain to Oral Flora of Radiology Physician Assistant

We recently investigated three cases of bacterial meningitis that were reported from a midwestern radiology clinic where facemasks were not worn during spinal injection of contrast agent during myelography procedures. Using pulsed field gel electrophoresis we linked a case strain of S. salivarius to an oral specimen of a radiology physician assistant (RPA). We also used a real-time PCR assay to detect S. salivarius DNA within a culture-negative cerebrospinal fluid (CSF) specimen. Here we extend this investigation through using a nested PCR/sequencing strategy to link the culture-negative CSF specimen to the case strain. We also provide validation of the real-time PCR assay used, demonstrating that it is not solely specific for Streptococcus salivarius, but is also highly sensitive for detection of the closely related oral species Streptococcus vestibularis. Through using multilocus sequence typing and 16S rDNA sequencing we further strengthen the link between the CSF case isolate and the RPA carriage isolate. We also demonstrate that the newly characterized strains from this study are distinct from previously characterized S. salivarius strains associated with carriage and meningitis