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Overview of the Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT): mechanistic chamber studies on the oxidation of biogenic compounds

The Focused Isoprene eXperiment at the California Institute of Technology (FIXCIT) was a collaborative atmospheric chamber campaign that occurred during January 2014. FIXCIT is the laboratory component of a synergistic field and laboratory effort aimed toward (1) better understanding the chemical details behind ambient observations relevant to the southeastern United States, (2) advancing the knowledge of atmospheric oxidation mechanisms of important biogenic hydrocarbons, and (3) characterizing the behavior of field instrumentation using authentic standards. Approximately 20 principal scientists from 14 academic and government institutions performed parallel measurements at a forested site in Alabama and at the atmospheric chambers at Caltech. During the 4 week campaign period, a series of chamber experiments was conducted to investigate the dark- and photo-induced oxidation of isoprene, α-pinene, methacrolein, pinonaldehyde, acylperoxy nitrates, isoprene hydroxy nitrates (ISOPN), isoprene hydroxy hydroperoxides (ISOPOOH), and isoprene epoxydiols (IEPOX) in a highly controlled and atmospherically relevant manner. Pinonaldehyde and isomer-specific standards of ISOPN, ISOPOOH, and IEPOX were synthesized and contributed by campaign participants, which enabled explicit exploration into the oxidation mechanisms and instrument responses for these important atmospheric compounds. The present overview describes the goals, experimental design, instrumental techniques, and preliminary observations from the campaign. This work provides context for forthcoming publications affiliated with the FIXCIT campaign. Insights from FIXCIT are anticipated to aid significantly in interpretation of field data and the revision of mechanisms currently implemented in regional and global atmospheric models.
A physically based framework for modeling the organic fractionation of sea spray aerosol from bubble film Langmuir equilibria

The presence of a large fraction of organic matter in primary sea spray aerosol (SSA) can strongly affect its cloud condensation nuclei activity and interactions with marine clouds. Global climate models require new parameterizations of the SSA composition in order to improve the representation of these processes. Existing proposals for such a parameterization use remotely sensed chlorophyll a concentrations as a proxy for the biogenic contribution to the aerosol. However, both observations and theoretical considerations suggest that existing relationships with chlorophyll a, derived from observations at only a few locations, may not be representative for all ocean regions. We introduce a novel framework for parameterizing the fractionation of marine organic matter into SSA based on a competitive Langmuir adsorption equilibrium at bubble surfaces. Marine organic matter is partitioned into classes with differing molecular weights, surface excesses, and Langmuir adsorption parameters. The classes include a lipid-like mixture associated with labile dissolved organic carbon (DOC), a polysaccharide-like mixture associated primarily with semilabile DOC, a protein-like mixture with concentrations intermediate between lipids and polysaccharides, a processed mixture associated with recalcitrant surface DOC, and a deep abyssal humic-like mixture. Box model calculations have been performed for several cases of organic adsorption to illustrate the underlying concepts. We then apply the framework to output from a global marine biogeochemistry model, by partitioning total dissolved organic carbon into several classes of macromolecules. Each class is represented by model compounds with physical and chemical properties based on existing laboratory data. This allows us to globally map the predicted organic mass fraction of the nascent submicron sea spray aerosol. Predicted relationships between chlorophyll a and organic fraction are similar to existing empirical parameterizations, but can vary between biologically productive and nonproductive regions, and seasonally within a given region. Major uncertainties include the bubble film thickness at bursting, and the variability of organic surfactant activity in the ocean, which is poorly constrained. In addition, polysaccharides may enter the aerosol more efficiently than Langmuir adsorption would suggest. Potential mechanisms for enrichment of polysaccharides in sea spray include the formation of marine colloidal particles that may be more efficiently swept up by rising bubbles, and cooperative adsorption of polysaccharides with proteins or lipids. These processes may make important contributions to the aerosol, but are not included here. This organic fractionation framework is an initial step towards a closer linking of ocean biogeochemistry and aerosol chemical composition in Earth system models. Future work should focus on improving constraints on model parameters through new laboratory experiments or through empirical fitting to observed relationships in the real ocean and atmosphere, as well as on atmospheric implications of the variable composition of organic matter in sea spray.
Radiocarbon analysis of elemental and organic carbon in Switzerland during winter-smog episodes from 2008 to 2012 – Part 1: Source apportionment and spatial variability

While several studies have investigated winter-time air pollution with a wide range of concentration levels, hardly any results are available for longer time periods covering several winter-smog episodes at various locations; e.g., often only a few weeks from a single winter are investigated. Here, we present source apportionment results of winter-smog episodes from 16 air pollution monitoring stations across Switzerland from five consecutive winters. Radiocarbon (14C) analyses of the elemental (EC) and organic (OC) carbon fractions, as well as levoglucosan, major water-soluble ionic species and gas-phase pollutant measurements were used to characterize the different sources of PM10. The most important contributions to PM10 during winter-smog episodes in Switzerland were on average the secondary inorganic constituents (sum of nitrate, sulfate and ammonium = 41 ± 15%) followed by organic matter (OM) (34 ± 13%) and EC (5 ± 2%). The non-fossil fractions of OC (fNF,OC) ranged on average from 69 to 85 and 80 to 95% for stations north and south of the Alps, respectively, showing that traffic contributes on average only up to ~ 30% to OC. The non-fossil fraction of EC (fNF,EC), entirely attributable to primary wood burning, was on average 42 ± 13 and 49 ± 15% for north and south of the Alps, respectively. While a high correlation was observed between fossil EC and nitrogen oxides, both primarily emitted by traffic, these species did not significantly correlate with fossil OC (OCF), which seems to suggest that a considerable amount of OCF is secondary, from fossil precursors. Elevated fNF,EC and fNF,OC values and the high correlation of the latter with other wood burning markers, including levoglucosan and water soluble potassium (K+) indicate that residential wood burning is the major source of carbonaceous aerosols during winter-smog episodes in Switzerland. The inspection of the non-fossil OC and EC levels and the relation with levoglucosan and water-soluble K+ shows different ratios for stations north and south of the Alps (most likely because of differences in burning technologies) for these two regions in Switzerland.
Volatile organic compounds over Eastern Himalaya, India: temporal variation and source characterization using Positive Matrix Factorization

A first ever study on the characterization of volatile organic compounds (VOCs) has been made over a Himalayan high altitude station in India. A total of 18 VOCs (mono aromatics-BTEX (benzene, toluene, ethylbenzene, xylene), non-BTEX substituted aromatics and halocarbon) have been measured over Darjeeling (27.01° N, 88.15° E, 2200 m a.s.l.) in the eastern Himalaya in India during the period of July 2011–June 2012. The annual average concentration of the sum of 18 target VOCs (TVOC) was 376.3 ± 857.2 μg m−3. Monoaromatics had the highest contribution (72%) followed by other substituted aromatics (22%) and halocarbon (6%) compounds. Toluene was the most abundant VOC in the atmosphere of Darjeeling with the contribution of ~37% to TVOC followed by benzene (~21%), ethylbenzene (~9%) and xylenes (~6%). TVOC concentrations were highest during the postmonsoon season with minimum solar radiation and lowest during the premonsoon season with maximum solar radiation. Anthropogenic activities related mainly to tourists like diesel and gasoline emissions, biomass and coal burning, use of solvent and solid waste emissions were almost equal in both the seasons. Seasonal variation in TVOCs over Darjeeling was mainly governed by the incoming solar radiation rather than the emission sources. Source apportionment study using Positive Matrix Factorization (PMF) model indicated that major fraction of (~60%) TVOC were contributed by diesel and gasoline exhausts followed by solvent evaporation (18%) and other sources. Diesel exhaust was also found to have the maximum potential in tropospheric ozone formation. The atmospheric loading of BTEX over Darjeeling was found to be comparable with several Indian metro cities and much higher than other cities around the world.
A global process-based study of marine CCN trends and variability

Low-level clouds have a strong climate-cooling effect in oceanic regions due to the much lower albedo of the underlying sea surface. Marine clouds typically have low droplet concentrations, making their radiative properties susceptible to changes in cloud condensation nucleus (CCN) concentrations. Here, we use the global aerosol model GLOMAP to investigate the processes that determine variations in marine CCN concentrations, and focus especially on the effects of previously identified wind speed trends in recent decades. Although earlier studies have found a link between linear wind speed trends and CCN concentration, we find that the effects of wind speed trends identified using a dynamic linear model in the Northern Equatorial Pacific (0.56 m s−1 per decade in the period 1990–2004) and the North Atlantic (−0.21 m s−1 per decade) are largely dampened by other processes controlling the CCN concentration, namely nucleation scavenging and transport of continental pollution. A CCN signal from wind speed change is seen only in the most pristine of the studied regions, i.e. over the Southern Ocean, where we simulate 3.4 cm−3 and 0.17 m s−1 increases over the 15-year period in the statistical mean levels of CCN and wind speed, respectively. Our results suggest that future changes in wind-speed-driven aerosol emissions from the oceans can probably have a climate feedback via clouds only in the most pristine regions. On the other hand, a feedback mechanism via changing precipitation patterns and intensities could take place over most oceanic regions, as we have shown that nucleation scavenging has by far the largest absolute effect on CCN concentrations.
Atmospheric oxidation of 1,3-butadiene: characterization of gas and aerosol reaction products and implications for PM2.5

Secondary organic aerosol (SOA) was generated by irradiating 1,3-butadiene (13BD) in the presence of H2O2 or NOx. Experiments were conducted in a smog chamber operated in either flow or batch mode. A filter/denuder sampling system was used for simultaneously collecting gas- and particle-phase products. The chemical composition of the gas phase and SOA was analyzed using derivative-based methods (BSTFA, BSTFA + PFBHA, or DNPH) followed by gas chromatography–mass spectrometry (GC–MS) or high-performance liquid chromatography (HPLC) analysis of the derivative compounds. The analysis showed the occurrence of more than 60 oxygenated organic compounds in the gas and particle phases, of which 31 organic monomers were tentatively identified. The major identified products include glyceric acid, d-threitol, erythritol, d-threonic acid, meso-threonic acid, erythrose, malic acid, tartaric acid, and carbonyls including glycolaldehyde, glyoxal, acrolein, malonaldehyde, glyceraldehyde, and peroxyacryloyl nitrate (APAN). Some of these were detected in ambient PM2.5 samples, and could potentially serve as organic markers of 13BD. Furthermore, a series of oligoesters were detected and found to be produced through chemical reactions occurring in the aerosol phase between compounds bearing alcoholic groups and compounds bearing acidic groups. SOA was analyzed for organic mass to organic carbon (OM /OC) ratio, effective enthalpy of vaporization (Δ Hvapeff), and aerosol yield. The average OM /OC ratio and SOA density were 2.7 ± 0.09 and 1.2 ± 0.05, respectively. The average Δ Hvapeff was −26.08 ± 1.46 kJ mol−1, a value lower than that of isoprene SOA. The average laboratory SOA yield measured in this study at aerosol mass concentrations between 22.5 and 140.2 μg m−3 was 0.025 ± 0.011, a value consistent with the literature (0.021–0.178). While the focus of this study has been examination of the particle-phase measurements, the gas-phase photooxidation products have also been examined. The contribution of SOA products from 13BD oxidation to ambient PM2.5 was investigated by analyzing a series of ambient PM2.5 samples collected in several locations around the United States. In addition to the occurrence of several organic compounds in field and laboratory samples, glyceric acid, d-threitol, erythritol, erythrose, and threonic acid were found to originate only from the oxidation of 13BD based on our previous experiments involving chamber oxidation of a series of hydrocarbons. Initial attempts have been made to quantify the concentrations of these compounds. The average concentrations of these compounds in ambient PM2.5 samples from the California Research at the Nexus of Air Quality and Climate Change (CalNex) study ranged from 0 to approximately 14.1 ng m−3. The occurrence of several other compounds in both laboratory and field samples suggests that SOA originating from 13BD oxidation could contribute to the ambient aerosol mainly in areas with high 13BD emission rates.
The contribution of plume-scale nucleation to global and regional aerosol and CCN concentrations: evaluation and sensitivity to emissions changes

We implement the Predicting Particles Produced in Power-Plant Plumes (P6) sub-grid sulphate parameterization for the first time into a global chemical-transport model with online aerosol microphysics, the GEOS-Chem-TOMAS model. Compared to simulations using two other previous treatments of sub-grid sulphate, simulations using P6 sub-grid sulphate predicted similar or smaller increases (depending on other model assumptions) in globally, annually averaged concentrations of particles larger than 80 nm (N80). We test in simulations using P6 sub-grid sulphate the sensitivity of particle number concentrations to changes in SO2 or NOx emissions to represent recent emissions control changes. For global increases of 50% in emissions of either SO2 or NOx, or both SO2 and NOx, we find that globally, annually averaged N80 increase by 9.00, 1.47, or 10.24% respectively. However, both sub-grid and grid-resolved processes contribute to these changes. Finally, we compare the model results against observations of particle number concentrations. Compared with previous treatments of sub-grid sulphate, use of the P6 parameterization generally improves correlation with observed particle number concentrations. The P6 parameterization is able to resolve spatial heterogeneity in new-particle formation and growth that cannot be resolved by any constant assumptions about sub-grid sulphate. However, the differences in annually averaged aerosol size distributions due to the treatment of sub-grid sulphate at the measurement sites examined here are too small to unambiguously establish P6 as providing better agreement with observations.
Biotic stress: a significant contributor to organic aerosol in Europe?

We have investigated the potential impact on organic aerosol formation from biotic stress-induced emissions (SIE) of organic molecules from forests in Europe (north of lat. 45° N). Emission estimates for sesquiterpenes (SQT), methyl salicylate (MeSA) and unsaturated C17 compounds, due to different stressors, are based on experiments in the Jülich Plant Atmosphere Chamber (JPAC), combined with estimates of the fraction of stressed trees in Europe based on reported observed tree damage. SIE were introduced in the EMEP MSC-W chemical transport model and secondary organic aerosol (SOA) yields from the SIE were taken from the JPAC experiments. Based on estimates of current levels of infestation and the JPAC aerosol yields, the model results suggest that the contribution to SOA in large parts of Europe may be substantial. It is possible that SIE contributes as much, or more, to organic aerosol than the constitutive biogenic VOC emissions, at least during some periods. Based on the assumptions in this study, SIE-SOA are estimated to constitute between 50 and 70 % of the total biogenic SOA (BSOA) in a current-situation scenario where the biotic stress in northern and central European forests causes large SIE of MeSA and SQT. An alternative current-situation scenario with lower SIE, consisting solely of SQT, leads to lower SIE-SOA, between 20 and 40 % of the total BSOA. Hypothetical future scenarios with increased SIE, due to higher degrees of biotic stress, show that SOA formation due to SIE can become even larger. Unsaturated C17 BVOC (biogenic volatile organic compounds) emitted by spruce infested by the forest-honey generating bark louse, Cinara pilicornis, have a high SOA-forming potential. A model scenario investigating the effect of a regional, episodic infestation of Cinara pilicornis in Baden-Württemberg, corresponding to a year with high production of forest honey, shows that these types of events could lead to very large organic aerosol formation in the infested region. We have used the best available laboratory data on biotic SIE applicable to northern and central European forests. Using these data and associated assumptions, we have shown that SIE are potentially important for SOA formation but the magnitude of the impact is uncertain and needs to be constrained by further laboratory, field and modelling studies. As an example, the MeSA, which is released as a consequence of various types of biotic stress, is found to have a potentially large impact on SIE-SOA in Europe, but different assumptions regarding the nighttime chemistry of MeSA can change its SOA potential substantially. Thus, further investigations of the atmospheric chemistry of MeSA and observational field studies are needed to clarify the role of this compound in the atmosphere.
The diurnal variation in stratospheric ozone from the MACC reanalysis, the ERA-Interim reanalysis, WACCM and Earth observation data: characteristics and intercomparison

In this study we compare the diurnal variation in stratospheric ozone derived from free-running simulations of the Whole Atmosphere Community Climate Model (WACCM) and from reanalysis data of the atmospheric service MACC (Monitoring Atmospheric Composition and Climate) which both use a similar stratospheric chemistry module. We find good agreement between WACCM and the MACC reanalysis for the diurnal ozone variation in the high-latitude summer stratosphere based on photochemistry. In addition, we consult the ozone data product of the ERA-Interim reanalysis. The ERA-Interim reanalysis ozone system with its long-term ozone parametrization can not capture these diurnal variations in the upper stratosphere that are due to photochemistry. The good dynamics representations, however, reflects well dynamically induced ozone variations in the lower stratosphere. For the high-latitude winter stratosphere we describe a novel feature of diurnal variation in ozone where changes of up to 46.6% (3.3 ppmv) occur in monthly mean data. For this effect good agreement between the ERA-Interim reanalysis and the MACC reanalysis suggest quite similar diurnal advection processes of ozone. The free-running WACCM model seriously underestimates the role of diurnal advection processes at the polar vortex at the two tested resolutions. The intercomparison of the MACC reanalysis and the ERA-Interim reanalysis demonstrates how global reanalyses can benefit from a chemical representation held by a chemical transport model. The MACC reanalysis provides an unprecedented description of the dynamics and photochemistry of the diurnal variation of stratospheric ozone which is of high interest for ozone trend analysis and research on atmospheric tides. We confirm the diurnal variation in ozone at 5 hPa by observations of the Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) experiment and selected sites of the Network for Detection of Atmospheric Composition Change (NDACC). The latter give valuable insight even to diurnal variation of ozone in the polar winter stratosphere.
Submicron aerosol source apportionment of wintertime pollution in Paris, France by double positive matrix factorization (PMF2) using an aerosol chemical speciation monitor (ACSM) and a multi-wavelength Aethalometer

Online non-refractory submicron aerosol mass spectrometer (AMS) measurements in urban areas have successfully allowed the apportionment of specific sources and/or physical and chemical properties of the organic fraction. However, in order to be fully representative of PM pollution, a comprehensive source apportionment analysis is needed by taking into account all major components of submicron aerosols, creating strengthened bonds between the organic components and pollution sources. We present here a novel two-step methodology to perform such an analysis, by taking advantage of high time resolution of monitoring instruments: the aerosol chemical speciation monitor (ACSM) and the multi-wavelength absorption measurements (Aethalometer AE31) in Paris, France. As a first step, organic aerosols (OA) were deconvolved to hydrocarbon-like OA (HOA), biomass burning OA (BBOA) and oxygenated OA (OOA) with positive matrix factorization (PMF), and black carbon was deconvolved into its wood burning and fossil fuel combustion fractions. A second PMF analysis was then carried out with organic factors, BC fractions and inorganic species (nitrate, sulfate, ammonium, chloride), leading to a four-factor solution allowing highly time-resolved characterization of the major sources of PM1. Outputs of this PMF2 include two dominant combustion sources (wood burning and traffic) as well as semi-volatile and low-volatile secondary aerosols. While HOA is found to be emitted by both wood burning and traffic, the latter sources occurred to significantly contribute also to OOA.