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Direct ecosystem fluxes of volatile organic compounds from oil palms in South-East Asia

This paper reports the first direct eddy covariance fluxes of reactive biogenic volatile organic compounds (BVOCs) from oil palms to the atmosphere using proton-transfer-reaction mass spectrometry (PTR-MS), measured at a plantation in Malaysian Borneo. At midday, net isoprene flux constituted the largest fraction (84 %) of all emitted BVOCs measured, at up to 30 mg m−2 h−1 over 12 days. By contrast, the sum of its oxidation products methyl vinyl ketone (MVK) and methacrolein (MACR) exhibited clear deposition of 1 mg m−2 h−1, with a small average canopy resistance of 230 s m−1. Approximately 15 % of the resolved BVOC flux from oil palm trees could be attributed to floral emissions, which are thought to be the largest reported biogenic source of estragole and possibly also toluene. Although on average the midday volume mixing ratio of estragole exceeded that of toluene by almost a factor of two, the corresponding fluxes of these two compounds were nearly the same, amounting to 0.81 and 0.76 mg m−2 h−1, respectively. By fitting the canopy temperature and PAR response of the MEGAN emissions algorithm for isoprene and other emitted BVOCs a basal emission rate of isoprene of 7.8 mg m−2 h−1 was derived. We parameterise fluxes of depositing compounds using a resistance approach using direct canopy measurements of deposition. Consistent with Karl et al. (2010), we also propose that it is important to include deposition in flux models, especially for secondary oxidation products, in order to improve flux predictions.
Source apportionment of size and time resolved trace elements and organic aerosols from an urban courtyard site in Switzerland

Time and size resolved data of trace elements were obtained from measurements with a rotating drum impactor (RDI) and subsequent X-ray fluorescence spectrometry. Trace elements can act as indicators for the identification of sources of particulate matter <10 μm (PM10) in ambient air. Receptor modeling was performed with positive matrix factorization (PMF) for trace element data from an urban background site in Zürich, Switzerland. Eight different sources were identified for the three examined size ranges (PM1−0.1, PM2.5−1 and PM10−2.5): secondary sulfate, wood combustion, fire works, road traffic, mineral dust, de-icing salt, industrial and local anthropogenic activities. The major component was secondary sulfate for the smallest size range; the road traffic factor was found in all three size ranges. This trace element analysis is complemented with data from an Aerodyne high-resolution time-of-flight aerosol mass spectrometer (AMS), assessing the PM1 fraction of organic aerosols. A separate PMF analysis revealed three factors related to three of the sources found with the RDI: oxygenated organic aerosol (OOA, related to inorganic secondary sulfate), hydrocarbon-like organic aerosol (HOA, related to road traffic) and biomass burning organic aerosol (BBOA), explaining 60 %, 22 % and 17 % of total measured organics, respectively. Since different compounds are used for the source classification, a higher percentage of the ambient PM10 mass concentration can be apportioned to sources by the combination of both methods.
Isotope effects in N2O photolysis from first principles

For the first time, accurate first principles potential energy surfaces allow N2O cross sections and isotopic fractionation spectra to be derived that are in agreement with all available experimental data, extending our knowledge to a much broader range of conditions. Absorption spectra of rare N- and O-isotopologues (15N14N16O, 14N15N16O, 15N216O, 14N217O and 14N218O) calculated using wavepacket propagation are compared to the most abundant isotopologue (14N216O). The fractionation constants as a function of wavelength and temperature are in excellent agreement with experimental data. The study shows that excitations from the 3rd excited bending state, (0,3,0), and the first combination state, (1,1,0), are important for explaining the isotope effect at wavelengths longer than 210 nm. Only a small amount of the mass independent oxygen isotope anomaly observed in atmospheric N2O samples can be explained as arising from photolysis.
Quantification of the volatility of secondary organic compounds in ultrafine particles during nucleation events

Condensation of secondary organic compounds onto ultrafine aerosols is important for growing these particles to sizes where they can act as cloud condensation nuclei. The organic flux to ultrafine particles depends strongly on the volatility of the condensing compounds. This paper presents quantitative estimates of the volatility of secondary organic aerosol (SOA) in freshly nucleated particles. We examine 13 nucleation/growth events in two remote continental locations, Hyytiälä, Finland and Egbert, ON, Canada. Two independent methods are used to quantify the volatility of the growing nucleation mode: (1) modelling of the growing nucleation mode to determine which volatilities allow the model to reproduce observed growth, and (2) modelling of the evaporation of heated aerosols in a Volatility Differential Mobility Particle Sizer to determine which volatilities allow the model to reproduce the observed evaporation. We find that the average saturation vapor concentration (C*) in the freshly nucleated particles (once Dp > 3 nm) is likely less than 10−3–10−2 μg m−3 (this corresponds to 3 × 106−3 × 107 molecules cm−3 and a saturation vapor pressure of 10−8–10−7 Pa). This maximum volatility depends somewhat on other uncertain factors that affect the size-dependent condensation of secondary organic compounds such as the surface tension, mass accommodation coefficient and the volatility of the pre-existing aerosols. However, our tests suggest that under no reasonable assumptions can the SOA in the ultrafine particles contain a majority of compounds with C* > 10−2 μg m−3. We demonstrate that the growth could be driven by either gas-phase or particle-phase chemistry but cannot conclude which is responsible for the low-volatility SOA.
On the relationship between low cloud variability and lower tropospheric stability in the Southeast Pacific

In this study, we examine marine low cloud cover variability in the Southeast Pacific and its association with lower-tropospheric stability (LTS) across a spectrum of timescales. On both daily and interannual timescales, LTS and low cloud amount are very well correlated in austral summer (DJF). Meanwhile in winter (JJA), when ambient LTS increases, the LTS–low cloud relationship substantially weakens. The DJF LTS–low cloud relationship also weakens in years with unusually large ambient LTS values. These are generally strong El Niño years, in which DJF LTS values are comparable to those typically found in JJA. Thus the LTS–low cloud relationship is strongly modulated by the seasonal cycle and the ENSO phenomenon. We also investigate the origin of LTS anomalies closely associated with low cloud variability during austral summer. We find that the ocean and atmosphere are independently involved in generating anomalies in LTS and hence variability in the Southeast Pacific low cloud deck. This highlights the importance of the physical (as opposed to chemical) component of the climate system in generating internal variability in low cloud cover. It also illustrates the coupled nature of the climate system in this region, and raises the possibility of cloud feedbacks related to LTS. We conclude by addressing the implications of the LTS–low cloud relationship in the Southeast Pacific for low cloud feedbacks in anthropogenic climate change.
Global cloud condensation nuclei influenced by carbonaceous combustion aerosol

Black carbon in carbonaceous combustion aerosol warms the climate by absorbing solar radiation, meaning reductions in black carbon emissions are often perceived as an attractive global warming mitigation option. However, carbonaceous combustion aerosol can also act as cloud condensation nuclei (CCN) so they also cool the climate by increasing cloud albedo. The net radiative effect of carbonaceous combustion aerosol is uncertain because their contribution to CCN has not been evaluated on the global scale. By combining extensive observations of CCN concentrations with the GLOMAP global aerosol model, we find that the model is biased low (normalised mean bias = −77 %) unless carbonaceous combustion aerosol act as CCN. We show that carbonaceous combustion aerosol accounts for more than half (52–64 %) of global CCN with the range due to uncertainty in the emitted size distribution of carbonaceous combustion particles. The model predicts that wildfire and pollution (fossil fuel and biofuel) carbonaceous combustion aerosol causes a global mean cloud albedo aerosol indirect effect of −0.34 W m−2, with stronger cooling if we assume smaller particle emission size. We calculate that carbonaceous combustion aerosol from pollution sources cause a global mean aerosol indirect effect of −0.23 W m−2. The small size of carbonaceous combustion particles from fossil fuel sources means that whilst pollution sources account for only one-third of the emitted mass they cause two-thirds of the cloud albedo aerosol indirect effect that is due to carbonaceous combustion aerosol. This cooling effect must be accounted for, along with other cloud effects not studied here, to ensure that black carbon emissions controls that reduce the high number concentrations of fossil fuel particles have the desired net effect on climate.
Interpreting methane variations in the past two decades using measurements of CH4 mixing ratio and isotopic composition

The availability δ13C-CH4 measurements from atmospheric samples has significantly improved in recent years, which allows the construction of time series spanning up to about 2 decades. We have used these measurements to investigate the cause of the methane growth rate decline since 1980, with a special focus on the period 1998–2006 when the methane growth came to a halt. The constraints provided by the CH4 and δ13C-CH4 measurements are used to construct hypothetical source and sink scenarios, which are translated into corresponding atmospheric concentrations using the atmospheric transport model TM3 for evaluation against the measurements. The base scenario, composed of anthropogenic emissions according to EDGAR 4.0, constant emissions from natural sources, and a constant atmospheric lifetime, overestimates the observed global growth rates of CH4 and δ13C-CH4 by, respectively, 10 ppb yr−1 and 0.02‰ yr−1 after the year 2000. It proves difficult to repair this inconsistency by modifying trends in emissions only, notably because a temporary reduction of isotopically light sources, such as natural wetlands, leads to a further increase of δ13C-CH4. Furthermore, our results are difficult to reconcile with the estimated increase of 5 Tg CH4 yr−1 in emissions from fossil fuel use in the period 2000–2005. On the other hand, we find that a moderate (less than 5% per decade) increase in the global OH concentration can bring the model in agreement with the measurements for plausible emission scenarios. This study demonstrates the value of global monitoring of methane isotopes, and calls for further investigation into the role OH and anthropogenic emissions to further improve our understanding of methane variations in recent years.
Airborne DOAS measurements in Arctic: vertical distributions of aerosol extinction coefficient and NO2 concentration

We report on airborne Differential Optical Absorption Spectroscopy (DOAS) measurements of aerosol extinction and NO2 tropospheric profiles performed off the North coast of Norway in April 2008. The DOAS instrument was installed on the Safire ATR-42 aircraft during the POLARCAT-France spring campaign and recorded scattered light spectra in near-limb geometry using a scanning telescope. We use O4 slant column measurements to derive the aerosol extinction at 360 nm. Regularization is based on the maximum a posteriori solution, for which we compare a linear and a logarithmic approach. The latter inherently constrains the solution to positive values and yields aerosol extinction profiles more consistent with independently measured size distributions. We present results from two soundings performed on 8 April 2008 above 71° N, 22° E and on 9 April 2008 above 70° N, 17.8° E. The first profile shows aerosol extinction and NO2 in the marine boundary layer with respective values of 0.04 ± 0.005 km−1 and 1.9 ± 0.3 × 109 molec cm−3. A second extinction layer of 0.01 ± 0.003 km−1 is found at 4 km altitude where the NO2 concentration is 0.32 ± 0.2 × 109 molec cm−3. During the second sounding, clouds prevent retrieval of profile parts under 3 km altitude but a layer with enhanced extinction (0.025 ± 0.005 km−1) and NO2 (1.95 ± 0.2 × 109 molec cm−3) is clearly detected at 4 km altitude. From CO and ozone in-situ measurements complemented by back-trajectories, we interpret the measurements in the free troposphere as, for the first sounding, a mix between stratospheric and polluted air from Northern Europe and for the second sounding, polluted air from Central Europe containing NO2. Considering the boundary layer measurements of the first flight, modeled source regions indicate closer sources, especially the Kola Peninsula smelters, which can explain the NO2 enhancement not correlated with a CO increase at the same altitude.
New and extended parameterization of the thermodynamic model AIOMFAC: calculation of activity coefficients for organic-inorganic mixtures containing carboxyl, hydroxyl, carbonyl, ether, ester, alkenyl, alkyl, and aromatic functional groups

We present a new and considerably extended parameterization of the thermodynamic activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficients) at room temperature. AIOMFAC combines a Pitzer-like electrolyte solution model with a UNIFAC-based group-contribution approach and explicitly accounts for interactions between organic functional groups and inorganic ions. Such interactions constitute the salt-effect, may cause liquid-liquid phase separation, and affect the gas-particle partitioning of aerosols. The previous AIOMFAC version was parameterized for alkyl and hydroxyl functional groups of alcohols and polyols. With the goal to describe a wide variety of organic compounds found in atmospheric aerosols, we extend here the parameterization of AIOMFAC to include the functional groups carboxyl, hydroxyl, ketone, aldehyde, ether, ester, alkenyl, alkyl, aromatic carbon-alcohol, and aromatic hydrocarbon. Thermodynamic equilibrium data of organic-inorganic systems from the literature are critically assessed and complemented with new measurements to establish a comprehensive database. The database is used to determine simultaneously the AIOMFAC parameters describing interactions of organic functional groups with the ions H+, Li+, Na+, K+, NH4+, Mg2+, Ca2+, Cl−, Br−, NO3−, HSO4−, and SO42−. Detailed descriptions of different types of thermodynamic data, such as vapor-liquid, solid-liquid, and liquid-liquid equilibria, and their use for the model parameterization are provided. Issues regarding deficiencies of the database, types and uncertainties of experimental data, and limitations of the model, are discussed. The challenging parameter optimization problem is solved with a novel combination of powerful global minimization algorithms. A number of exemplary calculations for systems containing atmospherically relevant aerosol components are shown. Amongst others, we discuss aqueous mixtures of ammonium sulfate with dicarboxylic acids and with levoglucosan. Overall, the new parameterization of AIOMFAC agrees well with a large number of experimental datasets. However, due to various reasons, for certain mixtures important deviations can occur. The new parameterization makes AIOMFAC a versatile thermodynamic tool. It enables the calculation of activity coefficients of thousands of different organic compounds in organic-inorganic mixtures of numerous components. Models based on AIOMFAC can be used to compute deliquescence relative humidities, liquid-liquid phase separations, and gas-particle partitioning of multicomponent mixtures of relevance for atmospheric chemistry or in other scientific fields.
Further analyses of the decadal-scale responses and trends in middle and upper stratospheric ozone from SAGE II and HALOE

Stratospheric Aerosol and Gas Experiment (SAGE II) Version 6.2 ozone profiles are analyzed for their decadal-scale responses and linear trends in the middle and upper stratosphere from 1984 through 1998. The results are compared with those of SAGE II and of the Halogen Occultation Experiment (HALOE) for 1991–2005, reported previously by Remsberg and Lingenfelser (2010). The regression model fit to the data includes a periodic 11- term, and it is in-phase with that of the 11-yr solar uv-flux throughout most of the latitude/altitude domain of the middle and upper stratosphere. Max minus min responses for the upper stratosphere are of order 2% from the HALOE time series that are in terms of mixing ratio versus pressure. Max minus min responses are of order 4% from SAGE II in terms of number density versus altitude and for both 1984–1998 and 1991–2005, even though the concurrent linear trend term coefficients are much different for the two time spans. However, the analyzed 11-yr response from the SAGE II data of 1984–1998 lags that of the uv-flux by 1 to 2 yr in the tropical middle stratosphere, most likely due to the effects of ENSO forcings that are not represented in the regression models. The linear ozone trends in the upper stratosphere for 1991 to 2005 are of the order of −2 to −3%/decade from SAGE II and 0 to −1%/decade from HALOE. Those differences in the ozone trends must be principally due to the associated temperature trends for the analyzed data.