Complementary mass spectrometric techniques for the characterization of the organic fraction in atmospheric aerosols

Aerosol particles are strongly related to climate, air quality, visibility and human health issues. They contribute the largest uncertainty in the assessment of the Earth´s radiative budget, directly by scattering or absorbing solar radiation or indirectly by nucleating cloud droplets. The influence of aerosol particles on cloud related climatic effects essentially depends upon their number concentration, size and chemical composition. A major part of submicron aerosol consists of secondary organic aerosol (SOA) that is formed in the atmosphere by the oxidation of volatile organic compounds. SOA can comprise a highly diverse spectrum of compounds that undergo continuous chemical transformations in the atmosphere.rnThe aim of this work was to obtain insights into the complexity of ambient SOA by the application of advanced mass spectrometric techniques. Therefore, an atmospheric pressure chemical ionization ion trap mass spectrometer (APCI-IT-MS) was applied in the field, facilitating the measurement of ions of the intact molecular organic species. Furthermore, the high measurement frequency provided insights into SOA composition and chemical transformation processes on a high temporal resolution. Within different comprehensive field campaigns, online measurements of particular biogenic organic acids were achieved by combining an online aerosol concentrator with the APCI-IT-MS. A holistic picture of the ambient organic aerosol was obtained through the co-located application of other complementary MS techniques, such as aerosol mass spectrometry (AMS) or filter sampling for the analysis by liquid chromatography / ultrahigh resolution mass spectrometry (LC/UHRMS).rnIn particular, during a summertime field study at the pristine boreal forest station in Hyytiälä, Finland, the partitioning of organic acids between gas and particle phase was quantified, based on the online APCI-IT-MS and AMS measurements. It was found that low volatile compounds reside to a large extent in the gas phase. This observation can be interpreted as a consequence of large aerosol equilibration timescales, which build up due to the continuous production of low volatile compounds in the gas phase and/or a semi-solid phase state of the ambient aerosol. Furthermore, in-situ structural informations of particular compounds were achieved by using the MS/MS mode of the ion trap. The comparison to MS/MS spectra from laboratory generated SOA of specific monoterpene precursors indicated that laboratory SOA barely depicts the complexity of ambient SOA. Moreover, it was shown that the mass spectra of the laboratory SOA more closely resemble the ambient gas phase composition, indicating that the oxidation state of the ambient organic compounds in the particle phase is underestimated by the comparison to laboratory ozonolysis. These observations suggest that the micro-scale processes, such as the chemistry of aerosol aging or the gas-to-particle partitioning, need to be better understood in order to predict SOA concentrations more reliably.rnDuring a field study at the Mt. Kleiner Feldberg, Germany, a slightly different aerosol concentrator / APCI-IT-MS setup made the online analysis of new particle formation possible. During a particular nucleation event, the online mass spectra indicated that organic compounds of approximately 300 Da are main constituents of the bulk aerosol during ambient new particle formation. Co-located filter analysis by LC/UHRMS analysis supported these findings and furthermore allowed to determine the molecular formulas of the involved organic compounds. The unambiguous identification of several oxidized C 15 compounds indicated that oxidation products of sesquiterpenes can be important compounds for the initial formation and subsequent growth of atmospheric nanoparticles.rnThe LC/UHRMS analysis furthermore revealed that considerable amounts of organosulfates and nitrooxy organosulfates were detected on the filter samples. Indeed, it was found that several nitrooxy organosulfate related APCI-IT-MS mass traces were simultaneously enhanced. Concurrent particle phase ion chromatography and AMS measurements indicated a strong bias between inorganic sulfate and total sulfate concentrations, supporting the assumption that substantial amounts of sulfate was bonded to organic molecules.rnFinally, the comprehensive chemical analysis of the aerosol composition was compared to the hygroscopicity parameter kappa, which was derived from cloud condensation nuclei (CCN) measurements. Simultaneously, organic aerosol aging was observed by the evolution of a ratio between a second and a first generation biogenic oxidation product. It was found that this aging proxy positively correlates with increasing hygroscopicity. Moreover, it was observed that the bonding of sulfate to organic molecules leads to a significant reduction of kappa, compared to an internal mixture of the same mass fractions of purely inorganic sulfate and organic molecules. Concluding, it has been shown within this thesis that the application of modern mass spectrometric techniques allows for detailed insights into chemical and physico-chemical processes of atmospheric aerosols.rn

Quantitative determination of carbonaceous particle mixing state in Paris using single-particle mass spectrometer and aerosol mass spectrometer measurements

Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions. Single-particle mixing state information can be a powerful tool for assessing the relative impact of local and regional sources of ambient particulate matter in urban environments. However, quantitative mixing state data are challenging to obtain using single-particle mass spectrometers. In this study, the quantitative chemical composition of carbonaceous single particles has been determined using an aerosol time-of-flight mass spectrometer (ATOFMS) as part of the MEGAPOLI 2010 winter campaign in Paris, France. Relative peak areas of marker ions for elemental carbon (EC), organic aerosol (OA), ammonium, nitrate, sulfate and potassium were compared with concurrent measurements from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), a thermal-optical OCEC analyser and a particle into liquid sampler coupled with ion chromatography (PILS-IC). ATOFMS-derived estimated mass concentrations reproduced the variability of these species well (R-2 = 0.67-0.78), and 10 discrete mixing states for carbonaceous particles were identified and quantified. The chemical mixing state of HR-ToF-AMS organic aerosol factors, resolved using positive matrix factorisation, was also investigated through comparison with the ATOFMS dataset. The results indicate that hydrocarbon-like OA (HOA) detected in Paris is associated with two EC-rich mixing states which differ in their relative sulfate content, while fresh biomass burning OA (BBOA) is associated with two mixing states which differ significantly in their OA/EC ratios. Aged biomass burning OA (OOA(2)-BBOA) was found to be significantly internally mixed with nitrate, while secondary, oxidised OA (OOA) was associated with five particle mixing states, each exhibiting different relative secondary inorganic ion content. Externally mixed secondary organic aerosol was not observed. These findings demonstrate the range of primary and secondary organic aerosol mixing states in Paris. Examination of the temporal behaviour and chemical composition of the ATOFMS classes also enabled estimation of the relative contribution of transported emissions of each chemical species and total particle mass in the size range investigated. Only 22% of the total ATOFMS-derived particle mass was apportioned to fresh, local emissions, with 78% apportioned to regional/continental-scale emissions.

Intercomparison study of six HTDMAs: results and recommendations

We report on an inter-comparison of six different hygroscopicity tandem differential mobility analysers (HTDMAs). These HTDMAs are used worldwide in laboratories and in field campaigns to measure the water uptake of aerosol particles and were never intercompared. After an investigation of the different design of the instruments with their advantages and inconveniencies, the methods for calibration, validation and analysis are presented. Measurements of nebulised ammonium sulphate as well as of secondary organic aerosol generated from a smog chamber were performed. Agreement and discrepancies between the instrument and to the theory are discussed, and final recommendations for a standard instrument are given, as a benchmark for laboratory or field experiments to ensure a high quality of HTDMA data.

Ozone-initiated particle formation, particle aging, and precursors in a laser printer

An increasing number of researchers have hypothesized that ozone may be involved in the particle formation processes that occur during printing, however no studies have investigated this further. In the current study, this hypothesis was tested in a chamber study by adding supplemental ozone to the chamber after a print job without measurable ozone emissions. Subsequent particle number concentration and size distribution measurements showed that new particles were formed minutes after the addition of ozone. The results demonstrated that ozone did react with printer-generated volatile organic compounds (VOCs) to form secondary organic aerosols (SOAs). The hypothesis was further confirmed by the observation of correlations among VOCs, ozone, and particles concentrations during a print job with measurable ozone emissions. The potential particle precursors were identified by a number of furnace tests, which suggested that squalene and styrene were the most likely SOA precursors with respect to ozone. Overall, this study significantly improved scientific understanding of the formation mechanisms of printer-generated particles, and highlighted the possible SOA formation potential of unsaturated nonterpene organic compounds by ozone-initiated reactions in the indoor environment. © 2011 American Chemical Society.

Effect of atmospheric aging on volatility and reactive oxygen species of biodiesel exhaust nano-particles

In the prospect of limited energy resources and climate change, effects of alternative biofuels on primary emissions are being extensively studied. Our two recent studies have shown that biodiesel fuel composition has a significant impact on primary particulate matter emissions. It was also shown that particulate matter caused by biodiesels was substantially different from the emissions due to petroleum diesel. Emissions appeared to have higher oxidative potential with the increase in oxygen content and decrease of carbon chain length and unsaturation levels of fuel molecules. Overall, both studies concluded that chemical composition of biodiesel is more important than its physical properties in controlling exhaust particle emissions. This suggests that the atmospheric aging processes, including secondary organic aerosol formation, of emissions from different fuels will be different as well. In this study, measurements were conducted on a modern common-rail diesel engine. To get more information on realistic properties of tested biodiesel particulate matter once they are released into the atmosphere, particulate matter was exposed to atmospheric oxidants, ozone and ultra-violet light; and the change in their properties was monitored for different biodiesel blends. Upon the exposure to oxidative agents, the chemical composition of the exhaust changes. It triggers the cascade of photochemical reactions resulting in the partitioning of semi-volatile compounds between the gas and particulate phase. In most of the cases, aging lead to the increase in volatility and oxidative potential, and the increment of change was mainly dependent on the chemical composition of fuels as the leading cause for the amount and the type of semi-volatile compounds present in the exhaust.

Broadband optical cavity absorption spectroscopy in the near-ultraviolet: applications in atmospheric chemistry

A novel spectroscopic method, incoherent broadband cavity enhanced absorption spectroscopy (IBBCEAS), has been modified and extended to measure absorption spectra in the near-ultraviolet with high sensitivity. The near-ultraviolet region extends from 300 to 400 nm and is particularly important in tropospheric photochemistry; absorption of near-UV light can also be exploited for sensitive trace gas measurements of several key atmospheric constituents. In this work, several IBBCEAS instruments were developed to record reference spectra and to measure trace gas concentrations in the laboratory and field. An IBBCEAS instrument was coupled to a flow cell for measuring very weak absorption spectra between 335 and 375 nm. The instrument was validated against the literature absorption spectrum of SO2. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably owing to the extremely weak absorption. The instrument was also applied to quantifying low concentrations of the short-lived radical, BrO, in the presence of strong absorption by Br2 and O3. A different IBBCEAS system was adapted to a 4 m3 atmosphere simulation chamber to record the absorption cross-sections of several low vapour pressure compounds, which are otherwise difficult to measure. Absorption cross-sections of benzaldehyde and the more volatile alkyl nitrites agree well with previous spectra; on this basis, the cross-sections of several nitrophenols are reported for the first time. In addition, the instrument was also used to study the optical properties of secondary organic aerosol formed following the photooxidation of isoprene. An extractive IBBCEAS instrument was developed for detecting HONO and NO2 and had a sensitivity of about 10-9 cm-1. This instrument participated in a major international intercomparison of HONO and NO2 measurements held in the EUPHORE simulation chamber in Valencia, Spain, and results from that campaign are also reported here.

Simulation chamber studies of the atmospheric degradation of naphthalene, 1-nitronaphthalene and phthaldialdehyde

A detailed series of simulation chamber experiments has been performed on the atmospheric degradation pathways of the primary air pollutant naphthalene and two of its photooxidation products, phthaldialdehyde and 1-nitronaphthalene. The measured yields of secondary organic aerosol (SOA) arising from the photooxidation of naphthalene varied from 6-20%, depending on the concentrations of naphthalene and nitrogen oxides as well as relative humidity. A range of carbonyls, nitro-compounds, phenols and carboxylic acids were identified among the gas- and particle-phase products. On-line analysis of the chemical composition of naphthalene SOA was performed using aerosol time-of-flight mass spectrometry (ATOFMS) for the first time. The results indicate that enhanced formation of carboxylic acids may contribute to the observed increase in SOA yields at higher relative humidity. The photolysis of phthaldialdehyde and 1-nitronaphthalene was investigated using natural light at the European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficients were measured directly and used to confirm that photolysis is the major atmospheric loss process for these compounds. For phthaldialdehyde, the main gas-phase products were phthalide and phthalic anhydride. SOA yields in the range 2-11% were observed, with phthalic acid and dihydroxyphthalic acid identified among the particle phase products. The photolysis of 1-nitronaphthalene yielded nitric oxide and a naphthoxy radical which reacted to form several products. SOA yields in the range 57-71% were observed, with 1,4-naphthoquinone, 1-naphthol and 1,4-naphthalenediol identified in the particle phase. On-line analysis of the SOA generated in an indoor chamber using ATOFMS provided evidence for the formation of high-molecular-weight products. Further investigations revealed that these products are oxygenated polycyclic compounds most likely produced from the dimerization of naphthoxy radicals. These results of this work indicate that naphthalene is a potentially large source of SOA in urban areas and should be included in atmospheric models. The kinetic and mechanistic information could be combined with existing literature data to produce an overall degradation mechanism for naphthalene suitable for inclusion in photochemical models that are used to predict the effect of emissions on air quality.

On the diurnal cycle of urban aerosols, black carbon and the occurrence of new particle formation events in springtime Sao Paulo, Brazil

Large conurbations are a significant source of the anthropogenic pollution and demographic differences between cities that result in a different pollution burden. The metropolitan area of Sao Paulo (MASP, population 20 million) accounts for one fifth of the Brazilian vehicular fleet. A feature of MASP is the amount of ethanol used by the vehicular fleet, known to exacerbate air quality. The study describes the diurnal behaviour of the submicron aerosol and relies on total particle number concentration, particle number size distribution, light scattering and light absorption measurements. Modelled planetary boundary layer (PBL) depth and air mass movement data were used to aid the interpretation. During morning rush-hour, stagnant air and a shallow PBL height favour the accumulation of aerosol pollution. During clear-sky conditions, there was a wind shift towards the edge of the city indicating a heat island effect with implications on particulate pollution levels at the site. The median total particle number concentration for the submicron aerosol typically varied in the range 1.6 x 10(4)-3.2 x 10(4) cm(-3) frequently exceeding 4 x 10(4) cm-3 during the day. During weekdays, nucleation-mode particles are responsible for most of the particles by numbers. The highest concentrations of total particle number concentrations and black carbon (BC) were observed on Fridays. Median diurnal values for light absorption and light scattering (at 637 nm wavelength) varied in the range 12-33 Mm(-1) and 21-64 Mm(-1), respectively. The former one is equal to 1.8-5.0 mu g m(-3) of BC. The growth of the PBL, from the morning rush-hour until noon, is consistent with the diurnal cycle of BC mass concentrations. Weekday hourly median single-scattering albedo (omega(0)) varied in the range 0.59-0.76. Overall, this suggests a top of atmosphere (TOA) warming effect. However, considering the low surface reflectance of urban areas, for the given range of omega(0), the TOA radiative forcing can be either positive or negative for the sources within the MASP. On the average, weekend omega(0) values were 0.074 higher than during weekdays. During 11% of the days, new particle formation (NPF) events occurred. The analysed events growth rates ranged between 9 and 25 nm h(-1). Sulphuric acid proxy concentrations calculated for the site were less than 5% of the concentration needed to explain the observed growth. Thus, other vapours are likely contributors to the observed growth.

Chemically Resolved Particle Fluxes Over Tropical and Temperate Forests

Chemically resolved submicron (PM1) particlemass fluxes were measured by eddy covariance with a high resolution time-of-flight aerosolmass spectrometer over temperate and tropical forests during the BEARPEX-07 and AMAZE-08 campaigns. Fluxes during AMAZE-08 were small and close to the detection limit (<1 ng m−2 s−1) due to low particle mass concentrations (<1 μg m−3). During BEARPEX-07, concentrations were five times larger, with mean mid-day deposition fluxes of −4.8 ng m−2 s−1 for total nonrefractory PM1 (Vex,PM1 = −1 mm s−1) and emission fluxes of +2.6 ng m−2 s−1 for organic PM1 (Vex,org = +1 mm s−1). Biosphere–atmosphere fluxes of different chemical components are affected by in-canopy chemistry, vertical gradients in gas-particle partitioning due to canopy temperature gradients, emission of primary biological aerosol particles, and wet and dry deposition. As a result of these competing processes, individual chemical components had fluxes of varying magnitude and direction during both campaigns. Oxygenated organic components representing regionally aged aerosol deposited, while components of fresh secondary organic aerosol (SOA) emitted. During BEARPEX-07, rapid incanopy oxidation caused rapid SOA growth on the timescale of biosphere-atmosphere exchange. In-canopy SOA mass yields were 0.5–4%. During AMAZE-08, the net organic aerosol flux was influenced by deposition, in-canopy SOA formation, and thermal shifts in gas-particle partitioning.Wet deposition was estimated to be an order ofmagnitude larger than dry deposition during AMAZE-08. Small shifts in organic aerosol concentrations from anthropogenic sources such as urban pollution or biomass burning alters the balance between flux terms. The semivolatile nature of the Amazonian organic aerosol suggests a feedback in which warmer temperatures will partition SOA to the gas-phase, reducing their light scattering and thus potential to cool the region.

Laboratory study on the optical properties of absorbing atmospheric aerosols and field applications

The interaction between aerosols and sun light plays an important role in the radiative balance of Earth’s atmosphere. This interaction is obtained by measuring the removal (extinction), redistribution (scattering), and transformation into heat (absorption) of light by the aerosols; i.e. their optical properties. Knowledge of these properties is crucial for our understanding of the atmospheric system. rn Light absorption by aerosols is a major contributor to the direct and indirect effects on our climate system, and an accurate and sensitive measurement method is crucial to further our understanding. A homebuilt photoacoustic sensor (PAS), measuring at a 532nm wavelength, was fully characterized and its functionality validated for measurements of absorbing aerosols. The optical absorption cross-sections of absorbing polystyrene latex spheres, to be used as a standard for aerosol absorption measurements, were measured and compared to literature values. Additionally, a calibration method using absorbing aerosol of known complex refractive index was presented.rn A new approach to retrieve the effective broadband refractive indices (mbroad,eff) of aerosol particles by a white light aerosol spectrometer (WELAS) optical particle counter (OPC) was achieved. Using a tandem differential mobility analyzer (DMA)-OPC system, the nbroad,eff are obtained for both laboratory and field applications. This method was tested in the laboratory using substances with a wide range of optical properties and it was used in ambient measurements to retrieve the nbroad,eff of biomass burning aerosols in a nationwide burning event in Israel. The retrieved effective broadband refractive indices for laboratory generated scattering aerosols were: ammonium sulfate (AS), glutaric acid (GA), and sodium chloride, all within 4% of literature values. For absorbing substances, nigrosine and various mixtures of nigrosine with AS and GA were measured, as well as a lightly absorbing substance, Suwannee river fulvic acid (SRFA). For the ambient measurements, the calibration curves generated from this method were to follow the optical evolution of biomass burning (BB) aerosols. A decrease in the overall aerosol absorption and scattering for aged aerosols during the day after the fires compared to the smoldering phase of the fires was found. rn The connection between light extinction of aerosols, their chemical composition and hygroscopicity for particles with different degrees of absorption was studied. The extinction cross-section (σext) at 532nm for different mobility diameters was measured at 80% and 90% relative humidity (RH), and at an RH<10%. The ratio of the humidified aerosols to the dry ones, fRHext(%RH,Dry), is presented. For purely scattering aerosols, fRHext(%RH,Dry) is inversely proportional with size; this dependence was suppressed for lightly absorbing ones. In addition, the validity of the mixing rules for water soluble absorbing aerosols is explored. The difference between the derived and calculated real parts of the complex RIs were less than 5.3% for all substances, wavelengths, and RHs. The obtained imaginary parts for the retrieved and calculated RIs were in good agreement with each other, and well within the measurement errors of retrieval from pulsed CRD spectroscopy measurements. Finally, a core-shell structure model is also used to explore the differences between the models, for substances with low growth factors, under these hydration conditions. It was found that at 80% RH and for size parameters less than 2.5, there is less than a 5 % difference between the extinction efficiencies calculated with both models. This difference is within measurement errors; hence, there is no significant difference between the models in this case. However, for greater size parameters the difference can be up to 10%. For 90% RH the differences below a size parameter of 2.5 were up to 7%.rn Finally, the fully characterized PAS together with a cavity ring down spectrometer (CRD), were used to study the optical properties of soot and secondary organic aerosol (SOA) during the SOOT-11 project in the AIDA chamber in Karlsruhe, Germany. The fresh fractal-like soot particles were allowed to coagulate for 28 hours before stepwise coating them with SOA. The single scattering albedo for fresh fractal-like soot was measured to be 0.2 (±0.03), and after allowing the soot to coagulate for 28 hours and coating it with SOA, it increased to 0.71(±0.01). An absorption enhancement of the coated soot of up to 1.71 (±0.03) times from the non-coated coagulated soot was directly measured with the PAS. Monodisperse measurements of SOA and soot coated with SOA were performed to derive the complex refractive index (m) of both aerosols. A complex refractive index of m = 1.471(±0.008) + i0.0(±0.002) for the SOA-αO3 was retrieved. For the compact coagulated soot a preliminary complex refractive index of m = 2.04(+0.21/-0.14) + i0.34(+0.18/-0.06) with 10nm(+4/-6) coating thickness was retrieved.rn These detail properties can be use by modelers to decrease uncertainties in assessing climatic impacts of the different species and to improve weather forecasting.rn

Laboratory and field measurements of enantiomeric and non-enantiomeric biogenic VOCs and anthropogenic BTEX compounds

This doctoral thesis was focused on the investigation of enantiomeric and non-enantiomeric biogenic organic compound (BVOC) emissions from both leaf and canopy scales in different environments. In addition, the anthropogenic compounds benzene, toluene, ethylbenzene, and xylenes (BTEX) were studied. BVOCs are emitted into the lower troposphere in large quantities (ca. 1150 Tg C ·yr-1), approximately an order of magnitude greater than the anthropogenic VOCs. BVOCs are particularly important in tropospheric chemistry because of their impact on ozone production and secondary organic aerosol formation or growth. The BVOCs examined in this study were: isoprene, (-)/ (+)-α-pinene, (-)/ (+)-ß-pinene, Δ-3-carene, (-)/ (+)-limonene, myrcene, eucalyptol and camphor, as these were the most abundant BVOCs observed both in the leaf cuvette study and the ambient measurements. In the laboratory cuvette studies, the sensitivity of enantiomeric enrichment change from the leaf emission has been examined as a function of light (0-1600 PAR) and temperature (20-45°C). Three typical Mediterranean plant species (Quercus ilex L., Rosmarinus officinalis L., Pinus halepensis Mill.) with more than three individuals of each have been investigated using a dynamic enclosure cuvette. The terpenoid compound emission rates were found to be directly linked to either light and temperature (e.g. Quercus ilex L.) or mainly to temperature (e.g. Rosmarinus officinalis L., Pinus halepensis Mill.). However, the enantiomeric signature showed no clear trend in response to either the light or temperature; moreover a large variation of enantiomeric enrichment was found during the experiment. This enantiomeric signature was also used to distinguish chemotypes beyond the normal achiral chemical composition method. The results of nineteen Quercus ilex L. individuals, screened under standard conditions (30°C and 1000 PAR) showed four different chemotypes, whereas the traditional classification showed only two. An enclosure branch cuvette set-up was applied in the natural boreal forest environment from four chemotypes of Scots pine (Pinus sylvestris) and one chemotype of Norway spruce (Picea abies) and the direct emissions compared with ambient air measurements above the canopy during the HUMPPA-COPEC 2010 summer campaign. The chirality of a-pinene was dominated by (+)-enantiomers from Scots pine while for Norway spruce the chirality was found to be opposite (i.e. Abstract II (-)-enantiomer enriched) becoming increasingly enriched in the (-)-enantiomer with light. Field measurements over a Spanish stone pine forest were performed to examine the extent of seasonal changes in enantiomeric enrichment (DOMINO 2008). These showed clear differences in chirality of monoterpene emissions. In wintertime the monoterpene (-)-a-pinene was found to be in slight enantiomeric excess over (+)-a-pinene at night but by day the measured ratio was closer to one i.e. racemic. Samples taken the following summer in the same location showed much higher monoterpene mixing ratios and revealed a strong enantiomeric excess of (-)-a-pinene. This indicated a strong seasonal variance in the enantiomeric emission ratio which was not manifested in the day/night temperature cycles in wintertime. A clear diurnal cycle of enantiomeric enrichment in a-pinene was also found over a French oak forest and the boreal forest. However, while in the boreal forest (-)-a-pinene enrichment increased around the time of maximum light and temperature, the French forest showed the opposite tendency with (+)-a-pinene being favored. For the two field campaigns (DOMINO 2008 and HUMPPA-COPEC 2010), the BTEX were also investigated. For the DOMINO campaign, mixing ratios of the xylene isomers (meta- and para-) and ethylbenzene, which are all well resolved on the ß-cyclodextrin column, were exploited to estimate average OH radical exposures to VOCs from the Huelva industrial area. These were compared to empirical estimates of OH based on JNO2 measured at the site. The deficiencies of each estimation method are discussed. For HUMPPA-COPEC campaign, benzene and toluene mixing ratios can clearly define the air mass influenced by the biomass burning pollution plume from Russia.

In-situ, satellite measurement and model evidence on the dominant regional contribution to fine particulate matter levels in the Paris Megacity

A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70% of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20%in winter and 40%in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies.

Gas/particle partitioning of carbonyls in the photooxidation of isoprene and 1,3,5-trimethylbenzene

A new denuder-filter sampling technique has been used to investigate the gas/particle partitioning behaviour of the carbonyl products from the photooxidation of isoprene and 1,3,5-trimethylbenzene. A series of experiments was performed in two atmospheric simulation chambers at atmospheric pressure and ambient temperature in the presence of NOx and at a relative humidity of approximately 50%. The denuder and filter were both coated with the derivatizing agent O-(2,3,4,5,6-pentafluorobenzyl)-hydroxylamine (PFBHA) to enable the efficient collection of gas- and particle-phase carbonyls respectively. The tubes and filters were extracted and carbonyls identified as their oxime derivatives by GC-MS. The carbonyl products identified in the experiments accounted for around 5% and 10% of the mass of secondary organic aerosol formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene respectively. Experimental gas/particle partitioning coefficients were determined for a wide range of carbonyl products formed from the photooxidation of isoprene and 1,3,5-trimethylbenzene and compared with the theoretical values based on standard absorptive partitioning theory. Photooxidation products with a single carbonyl moiety were not observed in the particle phase, but dicarbonyls, and in particular, glyoxal and methylglyoxal, exhibited gas/particle partitioning coefficients several orders of magnitude higher than expected theoretically. These findings support the importance of heterogeneous and particle-phase chemical reactions for SOA formation and growth during the atmospheric degradation of anthropogenic and biogenic hydrocarbons.