ALBERT

Description: More than 7000 atmospheric measurements of over 60 C2 − C16 volatile organic compounds (VOCs) were conducted at a background site in Cyprus during a 1-month intensive field campaign held in March 2015. This exhaustive dataset consisted of primary anthropogenic and biogenic VOCs, including a wide range of source-specific tracers, and oxygenated VOCs (with various origins) that were measured online by flame ionization detection–gas chromatography and proton transfer mass spectrometry. Online submicron aerosol chemical composition was performed in parallel using an aerosol mass spectrometer. This study presents the high temporal variability in VOCs and their associated sources. A preliminary analysis of their time series was performed on the basis of independent tracers (NO, CO, black carbon), meteorological data and the clustering of air mass trajectories. Biogenic compounds were mainly attributed to a local origin and showed compound-specific diurnal cycles such as a daily maximum for isoprene and a nighttime maximum for monoterpenes. Anthropogenic VOCs as well as oxygenated VOCs displayed higher mixing ratios under the influence of continental air masses (i.e., western Asia), indicating that long-range transport significantly contributed to the VOC levels in the area. Source apportionment was then conducted on a database of 20 VOCs (or grouped VOCs) using a source receptor model. The positive matrix factorization and concentration field analyses were hence conducted to identify and characterize covariation factors of VOCs that were representative of primary emissions as well as chemical transformation processes. A six-factor PMF solution was selected, namely two primary biogenic factors (relative contribution of 43 % to the total mass of VOCs) for different types of emitting vegetation; three anthropogenic factors (short-lived combustion source, evaporative sources, industrial and evaporative sources; 21 % all together), identified as being either of local origin or from more distant emission zones (i.e., the south coast of Turkey); and a last factor (36 %) associated with regional background pollution (air masses transported both from the Western and Eastern Mediterranean regions). One of the two biogenic and the regional background factors were found to be the largest contributors to the VOC concentrations observed at our sampling site. Finally, a combined analysis of VOC PMF factors with source-apportioned organic aerosols (OAs) helped to better distinguish between anthropogenic and biogenic influences on the aerosol and gas phase compositions. The highest OA concentrations were observed when the site was influenced by air masses rich in semi-volatile OA (less oxidized aerosols) originating from the southwest of Asia, in contrast with OA factor contributions associated with the remaining source regions. A reinforcement of secondary OA formation also occurred due to the intense oxidation of biogenic precursors.

Description: As a part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx) and Cyprus Aerosols and Gas Precursors (ENVI-Med CyAr) programs, this study aims primarily to provide an improved understanding of the sources and the fate of volatile organic compounds (VOCs) in the eastern Mediterranean. More than 60 VOCs, including biogenic species (isoprene and eight monoterpenes) and oxygenated VOCs, were measured during a 1-month intensive field campaign performed in March 2015 at the Cyprus Atmospheric Observatory (CAO), a regional background site in Cyprus. VOC measurements were conducted using complementary online and offline techniques. Biogenic VOCs (BVOCs) were principally imputed to local sources and characterized by compound-specific daily cycles such as diurnal maximum for isoprene and nocturnal maximum for α- and β-pinenes, in connection with the variability of emission sources. The simultaneous study of pinene and isoprene temporal evolution and meteorological parameters has shown that BVOC emissions were mainly controlled by ambient temperature, precipitation and relative humidity. It was found that isoprene daytime emissions at CAO depended on temperature and solar radiation changes, whereas nocturnal BVOC concentrations (e.g., from oak and pine forests) were more prone to the relative humidity and temperature changes. Significant changes in monoterpene mixing ratios occurred during and after rainfall. The second part of the study focused on new particle formation (NPF) events at CAO. BVOCs are known to potentially play a role in the growth as well as in the early stages of formation of new atmospheric particles. Based on observations of the particle size distribution performed with a differential mobility particle sizer (DMPS) and the total number concentrations of particles larger than 1 nm diameter measured by particle size magnifier (PSM), NPF events were found on 14 out of 20 days of the field campaign. For all possible proxy parameters (meteorological parameters, calculated H2SO4 and measured gaseous compounds) having a role in NPF, we present daily variations of different classes during nucleation event and non-event days. NPF can occur at various condensational sink (CS) values and both under polluted and clean atmospheric conditions. High H2SO4 concentrations coupled with high BVOC concentrations seemed to be one of the most favorable conditions to observe NPF at CAO in March 2015. NPF event days were characterized by either (1) a predominant anthropogenic influence (high concentrations of anthropogenic source tracers observed), (2) a predominant biogenic influence (high BVOC concentrations coupled with low anthropogenic tracer concentrations), (3) a mixed influence (high BVOC concentrations coupled with high anthropogenic tracer concentrations) and (4) a marine influence (both low BVOC and anthropogenic tracer concentrations). More pronounced NPF events were identified during mixed anthropogenic–biogenic conditions compared to the pure anthropogenic or biogenic ones, for the same levels of precursors. Analysis of a specific NPF period of the mixed influence type highlighted that BVOC interactions with anthropogenic compounds enhanced nucleation formation and growth of newly formed particles. During this period, the nucleation-mode particles may be formed by the combination of high H2SO4 and isoprene amounts, under favorable meteorological conditions (high temperature and solar radiation and low relative humidity) along with low CS. During the daytime, growth of the newly formed particles, not only sulfate but also oxygen-like organic aerosol (OOA) mass contributions, increased in the particle phase. High BVOC concentrations were observed during the night following NPF events, accompanied by an increase in CS and in semi-volatile OOA contributions, suggesting further BVOC contribution to aerosol nighttime growth by condensing onto pre-existing aerosols.

Description: Methylglyoxal (MGLY) is an important atmospheric α-dicarbonyl species for which photolysis acts as a significant source of peroxy radicals, contributing to the oxidizing capacity of the atmosphere and, as such, the formation of secondary pollutants such as organic aerosols and ozone. However, despite its importance, only a few techniques exhibit time resolutions and detection limits that are suitable for atmospheric measurements. This study presents the first field measurements of MGLY by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) performed during the ChArMEx SOP2 field campaign. This campaign took place at a Mediterranean site characterized by intense biogenic emissions and low levels of anthropogenic trace gases. Concomitant measurements of MGLY were performed using the 2,4-dinitrophenylhydrazine (DNPH) derivatization technique and high performance liquid chromatography (HPLC) with UV detection. PTR-ToF-MS and DNPH–HPLC measurements were compared to determine whether these techniques can perform reliable measurements of MGLY. Ambient time series revealed levels of MGLY ranging from 28 to 365 pptv, with a clear diurnal cycle due to elevated concentrations of primary biogenic species during the daytime, and its oxidation led to large production rates of MGLY. A scatter plot of the PTR-ToF-MS and DNPH–HPLC measurements indicates a reasonable correlation (R2=0.48) but a slope significantly lower than unity (0.58±0.05) and a significant intercept of 88.3±8.0 pptv. A careful investigation of the differences between the two techniques suggests that this disagreement is not due to spectrometric interferences from H3O+(H2O)3 or methyl ethyl ketone (or butanal) detected at m∕z 73.050 and m∕z 73.065, respectively, which are close to the MGLY m∕z of 73.029. The differences are more likely due to uncorrected sampling artifacts such as overestimated collection efficiency or loss of MGLY into the sampling line for the DNPH–HPLC technique or unknown isobaric interfering compounds such as acrylic acid and propanediol for the PTR-ToF-MS. Calculations of MGLY loss rates with respect to OH oxidation and direct photolysis indicate similar contributions for these two loss pathways.

Description: Exposure to particulate matter (PM) is leading to various respiratory health outcomes. Compared to coarse and fine particles, less is known about the effects of chronic exposure to ultrafine particles, despite their higher number and reactivity. In the present study, we performed a time-course experiment in mice to better analyze the lung impact of atmospheric ultrafine particles, with regard to the effects induced by fine particles collected on the same site. Trace element and PAH analysis demonstrated the almost similar chemical composition of both particle fractions. Mice were exposed intranasally to FF or UFP according to acute (10, 50 or 100 µg of PM) and repeated (10 µg of PM 3 times a week during 1 or 3 months) exposure protocols. More particle-laden macrophages and even greater chronic inflammation were observed in the UFP-exposed mice lungs. Histological analyses revealed that about 50% of lung tissues were damaged in mice exposed to UFP for three months versus only 35% in FF-exposed mice. These injuries were characterized by alveolar wall thickening, macrophage infiltrations, and cystic lesions. Taken together, these results strongly motivate the update of current regulations regarding ambient PM concentrations to include UFP and limit their emission.

Description: As a part of the ChArMEx (Chemistry Aerosol Mediterranean Experiments) and ENVI-Med CyAr (Cyprus aerosols and gas precursors) programs, this study aims primarily at providing an improved understanding of the sources and the fate of volatile organic compounds (VOCs) in the Eastern Mediterranean. More than 60 VOCs, including biogenic species (isoprene and 8 monoterpenes) and oxygenated VOCs were measured during a 1-month intensive field campaign performed in March 2015 at the Cyprus Atmospheric Observatory (CAO), a regional background site in Cyprus. VOC measurements were conducted using complementary on-line and off-line techniques. Biogenic (B)VOCs were principally imputed to local sources and characterized by compound-specific daily cycles such as diurnal maximum for isoprene and nocturnal maximum for α,β-pinenes, in connection with the variability of emission sources. The simultaneous study of pinenes and isoprene temporal evolution and meteorological parameters has shown that BVOC emissions were mainly controlled by ambient temperature, precipitation and relative humidity. It was found that isoprene daytime emissions at CAO depended on temperature and solar radiation changes whereas nocturnal BVOC concentrations (e.g. from oak and pine forests) were more prone on the relative humidity and temperature changes. Significant changes in monoterpene mixing ratios occurred during and after rain. The second part of the study focused on new particle formation events (NPF) at CAO. BVOCs are known to potentially play a role in the growth as well as in the early stages of formation of new atmospheric particles. Based on observations of the particle size distribution performed with a differential mobility particle sizer (DMPS) and the total number concentrations of particles larger than 1nm diameter measured by particle-size magnifier (PSM), NPF events were found on 14 out of 20 days of the field campaign. For all possible proxy parameters (meteorological parameters, calculated H2SO4 and measured gaseous compounds) having a role in NPF, we present daily variations of different classes during nucleation events and non-event days. NPF can occur at various condensational sink (CS) values and both under polluted and clean atmospheric conditions. High H2SO4 concentrations coupled with high BVOC concentrations seemed to be one of the most favorable conditions to observe NPF at CAO in March 2015. NPF event days were characterized by either (1) a predominant anthropogenic influence (high concentrations of anthropogenic source tracers observed), (2) a predominant biogenic influence (high BVOC concentrations coupled with low anthropogenic tracer concentrations), (3) a mixed influence (high BVOC concentrations coupled with high anthropogenic tracer concentrations) and (4) a marine influence (both low BVOC and anthropogenic concentrations). More pronounced NPF events were identified during mixed anthropogenic-biogenic conditions compared to the pure anthropogenic or biogenic ones, for the same levels of precursors. Analysis of specific NPF periods of the mixed influence type highlighted that BVOC interactions with anthropogenic compounds enhanced nucleation formation and growth of newly formed particles. During these days, the nucleation mode particles may be formed by the combination of high H2SO4 and isoprene amounts, under favorable meteorological conditions (high temperature and solar radiation and low relative humidity) and low CS. During the daytime, growth of the newly formed particles, sulfate but also oxygen-like organic aerosol (OOA) mass contributions increased in the particle phase. High BVOC concentrations were observed during the night following NPF events, accompanied with an increase of the CS and of semi volatile OOA contribution, suggesting further BVOC contribution to aerosol nighttime growth by condensing onto pre-existing aerosols.

Description: Methylglyoxal (MGLY) is an important atmospheric α-dicarbonyl species whose photolysis acts as a significant source of peroxy radicals, contributing to the oxidizing capacity of the atmosphere and, as such, the formation of secondary pollutants such as organic aerosols and ozone. However, despite its importance, only a few techniques exhibit time resolutions and detection limits that are suitable for atmospheric measurements. This study present, to the best of our knowledge, the first measurements of ambient MGLY using Proton Transfer Reaction-Time of Flight Mass Spectrometry (PTR-ToFMS). These measurements were performed during the ChArMEx SOP2 field campaign. This campaign took place at a Mediterranean site characterized by intense biogenic emissions and low levels of anthropogenic trace gases. Concomitant measurements of MGLY were performed using the 2,4-dinitrophenylhydrazine (DNPH) derivatization technique and High Performance Liquide Chromatography (HPLC) with UV detection. PTR-ToFMS and DNPH-HPLC measurements were compared to determine whether these techniques can perform reliable measurements of MGLY. Ambient time series revealed levels of MGLY ranging from 28–365pptv, with a clear diurnal cycle due to elevated concentrations of primary biogenic species during daytime, whose oxidation led to large production rates of MGLY. A scatter plot of the PTR-ToFMS and DNPH-HPLC measurements indicates a reasonable correlation (R2=0.48) but a slope significantly lower than unity (0.58±0.05) and a significant intercept of 88.3±8.0pptv. A careful investigation of the differences between the two techniques suggests that this disagreement is not due to spectrometric interferences from H3O+(H2O)3, MEK (or butanal) detected at m/z 73.050 and m/z 73.065, respectively, which are close to the MGLY m/z of 73.029. The differences are more likely due to uncorrected sampling artefacts such as overestimated collection efficiency or loss of MGLY into the sampling line for the DNPH-HPLC technique or unknown isobaric interfering compounds such as acrylic acid and propanediol for the PTR-ToFMS. Calculations of MGLY loss rates with respect to OH-oxidation and direct photolysis indicate similar contributions for these two loss pathways.

Description: More than 7,000 atmospheric measurements of over sixty C2-C16 Volatile Organic Compounds (VOCs) have been conducted at a background site in Cyprus during a 1-month intensive field campaign held in March 2015. This exhaustive dataset consisted in primary anthropogenic and biogenic VOCs, including a wide range of source-specific tracers, and oxygenated VOCs (originating from various origins) that were measured on-line by flame ionization detection/gas chromatography and proton transfer mass spectrometry. On-line submicron aerosol chemical composition was performed in parallel using an aerosol mass spectrometer. This study presents high temporal variability of VOCs and their associated sources. A preliminary analysis of their time series was performed on the basis of independent tracers (NO, CO, black carbon), meteorological data and clustering of air mass trajectories. Biogenic compounds were mainly attributed to be of local origin and showed compound-specific diurnal cycles such as daily maximum for isoprene and nighttime maximum for monoterpenes. Anthropogenic VOCs as well as oxygenated VOCs displayed higher mixing ratios under the influence of continental air masses (i.e. Western Asia) indicating that long-range transport significantly contributed to the VOC levels in the area. Source apportionment was then conducted on a database of 20 VOCs (or grouped VOCs) using a source receptor model. The positive matrix factorization and concentration field analyses were hence conducted to identify and characterize co-variation factors of VOCs that were representative of primary emissions as well as chemical transformation processes. A six-factor PMF solution was selected, namely two primary biogenic factors (relative contribution of 43 % to the total mass of VOCs) for different types of emitting vegetation; three anthropogenic factors (short-lived combustion source, evaporative sources, industrial and evaporative sources, 21 % all together), identified either of local origin but also from more distant emission zones (i.e. the south coasts of Turkey); and a last factor (36 %) associated to a regional background pollution (air masses transported both from Western and Eastern Mediterranean regions). One of the two biogenic and the regional background factors were found to be the largest contributors to the VOCs concentrations observed at our sampling site. Finally, a combined analysis of VOCs PMF factors with source apportioned organic aerosols (OA) helped to better distinguish between anthropogenic and biogenic influences on the aerosol and gas phase compositions. The highest OA concentrations were observed when the site was influenced by air masses rich in semi-volatile OA (less oxidized aerosols) originating from the Southwest of Asia, in contrast with OA factor contributions associated with the remaining source regions. A reinforcement of secondary OA formation also occurred due to intense oxidation of biogenic precursors.