Photochemical Aerosol Research Articles

An historical experiment: Los Angeles smog evolution observed by blimp

ABSTRACTObservations of smog over the Los Angeles Basin (LAB) links high oxidant mixing ratios with poor visibility, sometimes <5 km. By the 1970s, investigators recognized that most of the aerosol affecting visibility was from gaseous oxidation products, sulfate, nitrate, and organic carbon. This led to the 1972–1973 Aerosol Characterization Experiment (ACHEX), which included observations at the ground and from aircraft. Part of ACHEX was the measurement of smog by blimp in a Lagrangian-like format. The experiment on September 6, 1973, demonstrated that a blimp could travel with the wind across the LAB, observing ozone (O3) and precursors, and particles of different size ranges. These included condensation nuclei (CN) concentrations dominated by particles of ≤ 0.1 µm diameter and light scattering coefficient (bsc) representing mainly particles of 0.1–2.0 µm diameter. The results indicated a pollutant variation similar to that measured at a fixed site. Ozone was produced in an air mass, reaching a maximum of ~400 ppb in the presence of nitrogen oxides (NOx) and nonmethane hydrocarbons (NMHCs), then declined. Although the photochemistry was developing, bsc grew with O3 mixing ratio to a quasi-steady state at ~9–10 × 10−4 m−1, decreasing in value much later with decease in O3. The light scattering coefficient was found to be positively associated with the O3 mixing ratio, whereas CN concentrations were negatively proportional to O3 mixing ratio. The blimp experiment was supported with aircraft vertical profiles and ground-level observations from a mobile laboratory. The blimp flight obtained combined gas and particle changes aloft that could not be obtained by ground or fixed-wing aircraft measurements alone. The experiment was partially successful in achieving a true Lagrangian characterization of smog chemistry in a constrained or defined “open” air mass.Implications: The Los Angeles experiment demonstrated the use of a blimp as a platform for measurement of air pollution traveling with an air mass across an urban area. The method added unique data showing the relationship between photochemical smog chemistry and aerosol dynamics in smog. The method offers an alternative to reliance on smog chamber and modeling observations to designing air quality management strategies for reactive pollutants.

Variation in photon flux during extended photochemical aerosol experiments: Implications for atmospheric laboratory simulations

In order to simulate the interaction of sunlight with planetary atmospheres, including Pluto, Titan and the early Earth, many laboratory studies have used high-power broadband lamps with spectral features that extend into the vacuum-ultraviolet (VUV, <200 nm) to initiate photochemistry relevant to the atmosphere of interest. In many cases, experiments are run on the order of hundreds of hours with no accounting for how the photon flux within the system may be evolving with lamp age or a possible buildup of films over optical surfaces when working with high-yield photochemical systems. Given that the nature of photochemistry depends on the ratio of photons to reactants, variations in flux must be taken into account if the system is to be fully understood. In this study, standard N2O actinometry was used to measure the VUV flux of high-intensity deuterium lamps before, during, and after the photochemical synthesis of Titan analog aerosols made from methane or benzene precursors. It was found that VUV photon flux can be decreased by over 50% in under 10 h at higher number densities, with recorded flux losses of over 75% during extended (>60 h) photochemical experiments. While this is only one model system, it is apparent that changes in photon flux during simulations must be taken into account if adequate comparisons of the photochemical kinetics to their respective planetary environments are to be made.

Organic Aerosols in the Presence of CO2 in the Early Earth and Exoplanets: UV–Vis Refractive Indices of Oxidized Tholins

Abstract In this experimental study we investigate the role of atmospheric CO2 on the optical properties of organic photochemical aerosols. To this end, we add CO2 to a N2:CH4 gas mixture used in a plasma typically used for Titan studies. We produce organic thin films (tholins) in plasmas where the CO2/CH4 ratio is increased from 0 to 4. We measure these films via spectrometric ellipsometry and apply a Tauc–Lorentz model, used for optically transparent materials, to obtain the thickness of the thin film, its optical band gap, and the refractive indices in the UV–visible (270–600 nm). All samples present a significant absorption band in the UV. According to the Tauc–Lorentz model, as the CO2/CH4 ratio is quadrupled, the position of the UV band is shifted from ∼177 nm to 264 nm while its strength is quadrupled. Consequently, we infer that oxidized organic aerosols absorb more efficiently at longer UV wavelengths than reduced aerosols. Our laboratory wavelength-tabulated UV–vis refractive indices provide new constraints to atmospheric models of the early Earth and Earth-like exoplanets including photochemical hazes formed under increasingly oxidizing conditions.

Aerosol Properties of the Atmospheres of Extrasolar Giant Planets

Abstract We use a model of aerosol microphysics to investigate the impact of high-altitude photochemical aerosols on the transmission spectra and atmospheric properties of close-in exoplanets, such as HD 209458 b and HD 189733 b. The results depend strongly on the temperature profiles in the middle and upper atmospheres, which are poorly understood. Nevertheless, our model of HD 189733 b, based on the most recently inferred temperature profiles, produces an aerosol distribution that matches the observed transmission spectrum. We argue that the hotter temperature of HD 209458 b inhibits the production of high-altitude aerosols and leads to the appearance of a clearer atmosphere than on HD 189733 b. The aerosol distribution also depends on the particle composition, photochemical production, and atmospheric mixing. Due to degeneracies among these inputs, current data cannot constrain the aerosol properties in detail. Instead, our work highlights the role of different factors in controlling the aerosol distribution that will prove useful in understanding different observations, including those from future missions. For the atmospheric mixing efficiency suggested by general circulation models, we find that the aerosol particles are small (∼nm) and probably spherical. We further conclude that a composition based on complex hydrocarbons (soots) is the most likely candidate to survive the high temperatures in hot-Jupiter atmospheres. Such particles would have a significant impact on the energy balance of HD 189733 b’s atmosphere and should be incorporated in future studies of atmospheric structure. We also evaluate the contribution of external sources to photochemical aerosol formation and find that their spectral signature is not consistent with observations.

Heterogeneous reaction of peroxyacetyl nitrate (PAN) on soot

The interaction between photochemical oxidants and aerosol particles has been examined in previous atmospheric pollution studies. The heterogeneous reaction can affect the concentration of gases and free radicals, as well as the morphology and properties of particles. In this report, the interaction between the photochemical oxidant peroxyacetyl nitrate (PAN) and soot particles was investigated using a flow tube system. We used real-time online monitoring equipment to track changes in PAN concentrations. Substances on the soot surface were detected using ion chromatography (IC), x-ray photoelectron spectroscopy (XPS), and other surface analysis methods. At 295 K, the upper and lower limits of the initial uptake coefficients were 1.28 × 10−5 and 9.16 × 10−9, respectively. The heterogeneous reaction of PAN on soot was a first-order reaction to PAN under both dry and wet conditions. The products formed on soot included CH3COO−, HCOO−, NO2−, and NO3−. With an increase in relative humidity, the production of all species decreased and the relative amounts changed.

Development of an Automated System (PPWD/PILS) for Studying PM2.5 Water-Soluble Ions and Precursor Gases: Field Measurements in Two Cities, Taiwan

ABSTRACTAn automated system consisting of a particle-into-liquid sampler (PILS) and a parallel plate wet denuder (PPWD) coupled with an ion chromatography was used for simultaneous measurement of ambient water-soluble ions in PM2.5 and precursor gases. The performance of the PPWD/PILS was validated by comparing it with the PDS (porous metal denuder sampler) for precursor gases (NH3, HONO, HNO3 and SO2) and PM2.5 ionic species (NH4+, NO3–, SO42–, Na+, Cl– and K+) measured in Taipei and Hsinchu Cities of Taiwan. Good correlations were demonstrated with linear regression slopes ranging from 0.92 to 1.04 and 0.84 to 0.97 as well as R2 ranging from 0.76 to 0.83 and 0.89 to 0.94, for precursor gases and PM2.5 ions, respectively. The accuracy of the current system for precursor gases outperforms the other commercial systems. Field continuous data showed that NH3 was the most abundant precursor gas with the diurnal pattern peaking at low nocturnal boundary heights and during rush hours with local traffic emissions in Taipei, and with the pattern peaking only at mid-day associated with regional sources in Hsinchu. A reverse diurnal pattern for HONO in Taipei reflected the daytime photolysis and its nocturnal heterogeneous reaction, while its concentration was relatively constant at very low level in Hsinchu. SO42–, NH4+ and NO3– exhibited very similar diurnal patterns with the mean concentrations of 4.56 ± 3.14, 1.55 ± 1.16 and 0.52 ± 0.5 µg m–3 in Taipei, and 7.95 ± 5.52, 2.41 ± 1.95 and 0.96 ± 1.10 µg m–3 in Hsinchu, respectively. Correspondingly high concentrations of major ions to precursor gases were associated with the photochemical secondary aerosol formations and heavy traffic in Taipei. Based on an ammonia-rich atmosphere and high SOR values, (NH4)2SO4 and NH4NO3 were inferred to be the dominant inorganic salts in PM2.5 at both sites, which were also verified by the ion balance analysis.

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

Molecular composition and volatility of isoprene photochemical oxidation secondary organic aerosol under low- and high-NOx conditions

Investigation of furfural photolysis and photochemical aerosol formation kinetics

Investigation of furfural photolysis and photochemical aerosol formation kinetics

Follow the Carbon: Isotopic Labeling Studies of Early Earth Aerosol.

Despite the faint young Sun, early Earth might have been kept warm by an atmosphere containing the greenhouse gases CH4 and CO2 in mixing ratios higher than those found on Earth today. Laboratory and modeling studies suggest that an atmosphere containing these trace gases could lead to the formation of organic aerosol haze due to UV photochemistry. Chemical mechanisms proposed to explain haze formation rely on CH4 as the source of carbon and treat CO2 as a source of oxygen only, but this has not previously been verified experimentally. In the present work, we use isotopically labeled precursor gases and unit-mass resolution (UMR) and high-resolution (HR) aerosol mass spectrometry to examine the sources of carbon and oxygen to photochemical aerosol formed in a CH4/CO2/N2 atmosphere. UMR results suggest that CH4 contributes 70-100% of carbon in the aerosol, while HR results constrain the value from 94% to 100%. We also confirm that CO2 contributes approximately 10% of the total mass to the aerosol as oxygen. These results have implications for the geochemical interpretations of inclusions found in Archean rocks on Earth and for the astrobiological potential of other planetary atmospheres. Key Words: Atmosphere-Early Earth-Planetary atmospheres-Carbon dioxide-Methane. Astrobiology 16, 822-830.

Titan’s surface spectra at the Huygens landing site and Shangri-La

Titan is an icy satellite of Saturn with a dense atmosphere and covered by a global photochemical organic haze. Ground based observations and the Huygens descent probe allowed to retrieve the main spectral signature of the water ice (Griffith, C.A. et al. [2003]. Science 300(5619), 628–630; Coustenis, A. et al. [2005]. Icarus 177, 89–105) at the surface, possibly covered by a layer of sedimented organic material (Tomasko, M.G. et al. [2005]. Nature 438(7069), 765–778). However, the spectrum of the surface is not yet understood. In this study, we find that the surface reflectivity at the Huygens Landing Site (HLS) is well modeled by a layer of water ice grains overlaid by a moist layer of weakly compacted photochemical aggregated aerosols. Moist soils have spectra shifted toward short wavelengths relatively to spectra of dry soils. Cassini observations of Shangri-La region from orbit also show a very dark surface with a reflectivity peak shifted toward short wavelengths in respect to the reflectivity peak of bright surfaces, revealing a dichotomy between terrains based to their spectra in visible.

Impact of primary and secondary organic sources on the oxidative potential of quasi-ultrafine particles (PM0.25) at three contrasting locations in the Los Angeles Basin

To investigate the changing contribution of primary and secondary sources on the oxidative potential of particulate matter (PM) in a real-world urban atmosphere, 7 sets of quasi-ultrafine particles (PM0.25) were collected at three contrasting locations in the Los Angeles Basin, California, USA. Samples were collected in the coastal area of Long Beach during the morning rush hour period, representing fresh primary emissions from nearby freeways and the LA port; in central Los Angeles during midday, representing a mixture of fresh primary emissions and early products of photochemical secondary organic aerosol (SOA) formation; and at a downwind site (Upland) during afternoon, when the impacts of photochemically aged secondary PM are significant. Chemical composition showed distinctive trends, with the lowest fraction of water soluble organic carbon (WSOC) and other organic tracers of SOA formation (e.g. organic acids) at Long Beach, and the lowest abundance of organic tracers of primary vehicular emissions (such as polycyclic aromatic hydrocarbons and hopanes) at Upland. A molecular marker-based chemical mass balance (MM-CMB) model indicated that 72% of the total organic carbon at Long Beach was comprised of primary vehicular sources (combined heavy duty and light duty vehicles), while the vehicular fraction was found to be 50% and 39% at Los Angeles and Upland, respectively. Regression analysis suggested that at Long Beach, the variation in oxidative potential of PM0.25 (quantified using a macrophage-based reactive oxygen species (ROS) assay) was mainly driven by mobile vehicular emissions and the water-insoluble fraction of the organic carbon. In contrast, at Upland, where photochemical processing and secondary aerosol formation was the highest, WSOC and secondary organics were the major drivers of the oxidative potential variation. The multivariate regression analysis also indicated that as much as 58% of the overall spatial and temporal variation in the oxidative potential of PM0.25 at these three locations can be explained by mobile emissions and SOA.

Impact of isoprene and HONO chemistry on ozone and OVOC formation in a semirural South Korean forest

Abstract. Rapid urbanization and economic development in East Asia in past decades has led to photochemical air pollution problems such as excess photochemical ozone and aerosol formation. Asian megacities such as Seoul, Tokyo, Shanghai, Guangzhou, and Beijing are surrounded by densely forested areas, and recent research has consistently demonstrated the importance of biogenic volatile organic compounds (VOCs) from vegetation in determining oxidation capacity in the suburban Asian megacity regions. Uncertainties in constraining tropospheric oxidation capacity, dominated by hydroxyl radical, undermine our ability to assess regional photochemical air pollution problems. We present an observational data set of CO, NOx, SO2, ozone, HONO, and VOCs (anthropogenic and biogenic) from Taehwa research forest (TRF) near the Seoul metropolitan area in early June 2012. The data show that TRF is influenced both by aged pollution and fresh biogenic volatile organic compound emissions. With the data set, we diagnose HOx (OH, HO2, and RO2) distributions calculated using the University of Washington chemical box model (UWCM v2.1) with near-explicit VOC oxidation mechanisms from MCM v3.2 (Master Chemical Mechanism). Uncertainty from unconstrained HONO sources and radical recycling processes highlighted in recent studies is examined using multiple model simulations with different model constraints. The results suggest that (1) different model simulation scenarios cause systematic differences in HOx distributions, especially OH levels (up to 2.5 times), and (2) radical destruction (HO2 + HO2 or HO2 + RO2) could be more efficient than radical recycling (RO2 + NO), especially in the afternoon. Implications of the uncertainties in radical chemistry are discussed with respect to ozone–VOC–NOx sensitivity and VOC oxidation product formation rates. Overall, the NOx limited regime is assessed except for the morning hours (8 a.m. to 12 p.m. local standard time), but the degree of sensitivity can significantly vary depending on the model scenarios. The model results also suggest that RO2 levels are positively correlated with oxygenated VOCs (OVOCs) production that is not routinely constrained by observations. These unconstrained OVOCs can cause higher-than-expected OH loss rates (missing OH reactivity) and secondary organic aerosol formation. The series of modeling experiments constrained by observations strongly urge observational constraint of the radical pool to enable precise understanding of regional photochemical pollution problems in the East Asian megacity region.

13C and 15N fractionation of CH4/N2 mixtures during photochemical aerosol formation: Relevance to Titan

The ratios of the stable isotopes that comprise each chemical species in Titan’s atmosphere provide critical information towards understanding the processes taking place within its modern and ancient atmosphere. Several stable isotope pairs, including 12C/13C and 14N/15N, have been measured in situ or probed spectroscopically by Cassini-borne instruments, space telescopes, or through ground-based observations. Current attempts to model the observed isotope ratios incorporate fractionation resulting from atmospheric diffusion, hydrodynamic escape, and primary photochemical processes. However, the effect of a potentially critical pathway for isotopic fractionation – organic aerosol formation and subsequent deposition onto the surface of Titan – has not been considered due to insufficient data regarding fractionation during aerosol formation. To better understand the nature of this process, we have conducted a laboratory study to measure the isotopic fractionation associated with the formation of Titan aerosol analogs, commonly referred to as ‘tholins’, via far-UV irradiation of several methane (CH4) and dinitrogen (N2) mixtures. Analysis of the δ13C and δ15N isotopic signatures of the photochemical aerosol products using an isotope ratio mass spectrometer (IRMS) show that fractionation direction and magnitude are dependent on the initial bulk composition of the gas mixture. In general, the aerosols showed enrichment in 13C and 14N, and the observed fractionation trends can provide insight into the chemical mechanisms controlling photochemical aerosol formation.

Seasons on Saturn. I. Changes in reflecting characteristics of the atmosphere at 1964–2012

Due to considerable tilting of the equator to the orbital plane, presence of rings and elongation of the orbit around the Sun, Saturn is strongly affected by seasonal changes in the solar radiation influx. Such change of the mode of irradiation of Saturn's atmosphere should affect physical properties and optical characteristics of the cloud cover and/or haze above the clouds of the planet, as well as on the vertical structure of the atmosphere at different latitudes. Once in 14,7 terrestrial years we have the equality of conditions of insolation for both hemispheres, when the planet's rings are visible edge-on to a terrestrial observer. Therefore, these moments are interest for comparative study of possible differences in atmospheric characteristics of the northern and southern hemispheres. In recent years, possibilities for such observations were in 1966, 1980, 1995 and 2009. Using the observational data on the distribution of reflective characteristics of the atmosphere on the visible planetary disk, we have compared the results of calculations in the framework of a two-layer model of Saturn's atmosphere for above moments of equinoxes. It was found that in moments of equinox in 1966, 1980 and 1995 for spring hemisphere, which had just emerged from the rings shadow, the planetary latitudinal belts differ significantly from the other zones by the values of scattering component of the optical thickness τ_c of gas layer above the clouds, the volume concentration of aerosol cloud n, and imaginary part of refractive index n_i of cloud particles. But at the time of the equinox in 2009, in the spring hemisphere the expected changes of reflective and absorptive characteristics – did not happen. There methane absorption remained at the same high level and does not form any high-altitude haze and/or rarefied cloud layer. Because they have the photochemical nature, we can assume an insufficient amount of incoming energy into the atmosphere for the possibility of the formation a photochemical aerosol layer in the lower stratosphere and/or upper troposphere of Saturn.

The global nitrogen cycle in the twenty-first century

Global nitrogen fixation contributes 413 Tg of reactive nitrogen (Nr) to terrestrial and marine ecosystems annually of which anthropogenic activities are responsible for half, 210 Tg N. The majority of the transformations of anthropogenic Nr are on land (240 Tg N yr(-1)) within soils and vegetation where reduced Nr contributes most of the input through the use of fertilizer nitrogen in agriculture. Leakages from the use of fertilizer Nr contribute to nitrate (NO3(-)) in drainage waters from agricultural land and emissions of trace Nr compounds to the atmosphere. Emissions, mainly of ammonia (NH3) from land together with combustion related emissions of nitrogen oxides (NOx), contribute 100 Tg N yr(-1) to the atmosphere, which are transported between countries and processed within the atmosphere, generating secondary pollutants, including ozone and other photochemical oxidants and aerosols, especially ammonium nitrate (NH4NO3) and ammonium sulfate (NH4)2SO4. Leaching and riverine transport of NO3 contribute 40-70 Tg N yr(-1) to coastal waters and the open ocean, which together with the 30 Tg input to oceans from atmospheric deposition combine with marine biological nitrogen fixation (140 Tg N yr(-1)) to double the ocean processing of Nr. Some of the marine Nr is buried in sediments, the remainder being denitrified back to the atmosphere as N2 or N2O. The marine processing is of a similar magnitude to that in terrestrial soils and vegetation, but has a larger fraction of natural origin. The lifetime of Nr in the atmosphere, with the exception of N2O, is only a few weeks, while in terrestrial ecosystems, with the exception of peatlands (where it can be 10(2)-10(3) years), the lifetime is a few decades. In the ocean, the lifetime of Nr is less well known but seems to be longer than in terrestrial ecosystems and may represent an important long-term source of N2O that will respond very slowly to control measures on the sources of Nr from which it is produced.

Effect of the land use change characteristics on the air pollution patterns above the Greater Athens area (GAA) after 2004

The Attica Peninsula has experienced the rapid expansion of the Athens urban area, prior to the Athens 2004 Olympics. As a result, the distribution of pollutant sources and emission patterns has changed with a subsequent effect on the distribution of photochemical pollutants and aerosols. The purpose of the present work is to perform a comparative study of the land use changes in the rapidly developing Attica Peninsula including the Greater Athens Area (GAA) before and after 2004, the year that the Olympic Games took place, as well as of the effect of these changes on the respective pollutant distribution profiles. The land use data were provided by USGS Global Land Use/Land Cover version 2.0 Database and the updating process was fulfilled with the help of a satellite image. The area was divided into cells using a spatial resolution of 5x5 km2. Results showed that the urban grid has expanded considerably the past fifteen years while a great shift of population has been made to the eastern area of Attica. Also, new towns were created while others expanded and many factories moved out of the center of the city of Athens. Moreover, the forest land has decreased considerably in the Attica Peninsula either by continuous and extended fires or by the residential burst. The Comprehensive Air Quality Model with extensions (CAMx) was used in order to estimate O3 distribution during a recorded pollution episode. Results revealed that land use changes affected slightly the O3 concentrations and the development of a new emission inventory related to the new LULC field is necessary.

Aerosol growth in Titan’s ionosphere

Photochemically produced aerosols are common among the atmospheres of our solar system and beyond. Observations and models have shown that photochemical aerosols have direct consequences on atmospheric properties as well as important astrobiological ramifications, but the mechanisms involved in their formation remain unclear. Here we show that the formation of aerosols in Titan's upper atmosphere is directly related to ion processes, and we provide a complete interpretation of observed mass spectra by the Cassini instruments from small to large masses. Because all planetary atmospheres possess ionospheres, we anticipate that the mechanisms identified here will be efficient in other environments as well, modulated by the chemical complexity of each atmosphere.

Nocturnal isoprene emission from mature trees and diurnal acceleration of isoprene oxidation rates near Quercus serrata Thunb. leaves

Quercus serrata Thunb. ex Murray is a widespread deciduous oak in China, the Korean Peninsula, and Japan, and a strong isoprene emitter. Establishing accurate inventories of this species and estimating net carbon budgets, including biogenic volatile organic compounds (BVOC), necessitates detailed evaluation of BVOC emission and oxidation characteristics. Emissions of isoprene, the most abundant BVOC, presumably contribute to atmospheric chemistry through the formation of photochemical oxidants and secondary organic aerosols. We built an isoprene flux monitoring system to simultaneously reveal characteristics of the flux and fate of isoprene at multiple locations in Q. serrata forests. We used proton transfer reaction mass spectrometry (PTR-MS) and an automated closed chamber to measure isoprene emissions from soil and leaves in a warm-temperate Q. serrata forest. We used a relaxed eddy accumulation system with PTR-MS to simultaneously measure the canopy flux. In continuous foliage chamber measurements, we observed daily variations of isoprene emissions and continuous nocturnal emissions from leaves. Nocturnal emissions exceeded 25 % of total daily leaf emissions and were relatively high at sunset and low at sunrise. These results suggest that nocturnal emissions from mature trees may not be negligible. When leaf emissions were high in the daytime, the canopy isoprene flux tended to plateau at an upper limit. Observations of isoprene concentrations and gradients suggest that the plateau was caused by acceleration of isoprene oxidation, and sequential formation of secondary organic aerosols may occur near the leaf just after emission. Elucidation of these linkages may require continuous field measurements with a simultaneous multi-flux monitoring system.

Nitrogen Incorporation in CH4-N2 Photochemical Aerosol Produced by Far Ultraviolet Irradiation

Nitrile incorporation into Titan aerosol accompanying hydrocarbon chemistry is thought to be driven by extreme UV wavelengths (λ<120 nm) or magnetospheric electrons in the outer reaches of the atmosphere. Far UV radiation (120-200 nm), which is transmitted down to the stratosphere of Titan, is expected to affect hydrocarbon chemistry only and not initiate the formation of nitrogenated species. We examined the chemical properties of photochemical aerosol produced at far UV wavelengths, using a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS), which allows for elemental analysis of particle-phase products. Our results show that aerosol formed from CH(4)/N(2) photochemistry contains a surprising amount of nitrogen, up to 16% by mass, a result of photolysis in the far UV. The proportion of nitrogenated organics to hydrocarbon species is shown to be correlated with that of N(2) in the irradiated gas. The aerosol mass greatly decreases when N(2) is removed, which indicates that N(2) plays a major role in aerosol production. Because direct dissociation of N(2) is highly improbable given the immeasurably low cross section at the wavelengths studied, the chemical activation of N(2) must occur via another pathway. Any chemical activation of N(2) at wavelengths >120 nm is presently unaccounted for in atmospheric photochemical models. We suggest that reaction with CH radicals produced from CH(4) photolysis may provide a mechanism for incorporating N into the molecular structure of the aerosol. Further work is needed to understand the chemistry involved, as these processes may have significant implications for how we view prebiotic chemistry on early Earth and similar planets.

Isoprene in poplar emissions: effects on new particle formation and OH concentrations

Abstract. Stress-induced volatile organic compound (VOC) emissions from transgenic Grey poplar modified in isoprene emission potential were used for the investigation of photochemical secondary organic aerosol (SOA) formation. In poplar, acute ozone stress induces the emission of a wide array of VOCs dominated by sesquiterpenes and aromatic VOCs. Constitutive light-dependent emission of isoprene ranged between 66 nmol m−2 s−1 in non-transgenic controls (wild type WT) and nearly zero (&lt;0.5 nmol m−2 s−1) in isoprene emission-repressed plants (line RA22), respectively. Nucleation rates of up to 3600 cm−3 s−1 were observed in our experiments. In the presence of isoprene new particle formation was suppressed compared to non-isoprene containing VOC mixtures. Compared to isoprene/monoterpene systems emitted from other plants the suppression of nucleation by isoprene was less effective for the VOC mixture emitted from stressed poplar. This is explained by the observed high efficiency of new particle formation for emissions from stressed poplar. Direct measurements of OH in the reaction chamber revealed that the steady state concentration of OH is lower in the presence of isoprene than in the absence of isoprene, supporting the hypothesis that isoprenes' suppressing effect on nucleation is related to radical chemistry. In order to test whether isoprene contributes to SOA mass formation, fully deuterated isoprene (C5D8) was added to the stress-induced emission profile of an isoprene free poplar mutant. Mass spectral analysis showed that, despite the isoprene-induced suppression of particle formation, fractions of deuterated isoprene were incorporated into the SOA. A fractional mass yield of 2.3% of isoprene was observed. Future emission changes due to land use and climate change may therefore affect both gas phase oxidation capacity and new particle number formation.