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Dimethylsulphide (DMS) emissions from the western Pacific Ocean: a potential marine source for stratospheric sulphur?

Sea surface and atmospheric measurements of dimethylsulphide (DMS) were performed during the TransBrom cruise in the western Pacific Ocean between Japan and Australia in October 2009. Air–sea DMS fluxes were computed between 0 and 30 μmol m−2 d−1, which are in agreement with those computed by the current climatology, and peak emissions of marine DMS into the atmosphere were found during the occurrence of tropical storm systems. Atmospheric variability in DMS, however, did not follow that of the computed fluxes and was more related to atmospheric transport processes. The computed emissions were used as input fields for the Lagrangian dispersion model FLEXPART, which was set up with actual meteorological fields from ERA-Interim data and different chemical lifetimes of DMS. A comparison with aircraft in situ data from the adjacent HIPPO2 campaign revealed an overall good agreement between modelled versus observed DMS profiles over the tropical western Pacific Ocean. Based on observed DMS emissions and meteorological fields along the cruise track, the model projected that up to 30 g S per month in the form of DMS, emitted from an area of 6 × 104 m2, can be transported above 17 km. This surprisingly large DMS entrainment into the stratosphere is disproportionate to the regional extent of the area of emissions and mainly due to the high convective activity in this region as simulated by the transport model. Thus, if DMS can cross the tropical tropopause layer (TTL), we suggest that the considerably larger area of the tropical western Pacific Ocean can be a source of sulphur to the stratosphere, which has not been considered as yet.
Primary and secondary organic aerosol origin by combined gas-particle phase source apportionment

Secondary organic aerosol (SOA), a prominent fraction of particulate organic mass (OA), remains poorly constrained. Its formation involves several unknown precursors, formation and evolution pathways and multiple natural and anthropogenic sources. Here a combined gas-particle phase source apportionment is applied to wintertime and summertime data collected in the megacity of Paris in order to investigate SOA origin during both seasons. This was possible by combining the information provided by an aerosol mass spectrometer (AMS) and a proton transfer reaction mass spectrometer (PTR-MS). A better constrained apportionment of primary OA (POA) sources is also achieved using this methodology, making use of gas-phase tracers. These tracers made possible the discrimination between biogenic and continental/anthropogenic sources of SOA. We found that continental SOA was dominant during both seasons (24–50% of total OA), while contributions from photochemistry-driven SOA (9% of total OA) and marine emissions (13% of total OA) were also observed during summertime. A semi-volatile nighttime component was also identified (up to 18% of total OA during wintertime). This approach was successfully applied here and implemented in a new source apportionment toolkit.
Modeling microphysical effects of entrainment in clouds observed during EUCAARI-IMPACT field campaign

This paper discusses aircraft observations and large-eddy simulation (LES) modeling of 15 May 2008, North Sea boundary-layer clouds from the EUCAARI-IMPACT field campaign. These clouds are advected from the northeast by the prevailing lower-tropospheric winds and featured stratocumulus-over-cumulus cloud formations. An almost-solid stratocumulus deck in the upper part of the relatively deep, weakly decoupled marine boundary layer overlays a field of small cumuli. The two cloud formations have distinct microphysical characteristics that are in general agreement with numerous past observations of strongly diluted shallow cumuli on one hand and solid marine stratocumulus on the other. Based on the available observations, a LES model setup is developed and applied in simulations using a novel LES model. The model features a double-moment warm-rain bulk microphysics scheme combined with a sophisticated subgrid-scale scheme allowing local prediction of the homogeneity of the subgrid-scale turbulent mixing. The homogeneity depends on the characteristic time scales for the droplet evaporation and for the turbulent homogenization. In the model, these scales are derived locally based on the subgrid-scale turbulent kinetic energy, spatial scale of cloudy filaments, mean cloud droplet radius, and humidity of the cloud-free air entrained into a cloud, all predicted by the LES model. The model reproduces contrasting macrophysical and microphysical characteristics of the cumulus and stratocumulus cloud layers. Simulated subgrid-scale turbulent mixing within the cumulus layer and near the stratocumulus top is on average quite inhomogeneous, but varies significantly depending on the local conditions.
Understanding the impact of recent advances in isoprene photooxidation on simulations of regional air quality

The CMAQ (Community Multiscale Air Quality) us model in combination with observations for INTEX-NA/ICARTT (Intercontinental Chemical Transport Experiment–North America/International Consortium for Atmospheric Research on Transport and Transformation) 2004 are used to evaluate recent advances in isoprene oxidation chemistry and provide constraints on isoprene nitrate yields, isoprene nitrate lifetimes, and NOx recycling rates. We incorporate recent advances in isoprene oxidation chemistry into the SAPRC-07 chemical mechanism within the US EPA (United States Environmental Protection Agency) CMAQ model. The results show improved model performance for a range of species compared against aircraft observations from the INTEX-NA/ICARTT 2004 field campaign. We further investigate the key processes in isoprene nitrate chemistry and evaluate the impact of uncertainties in the isoprene nitrate yield, NOx (NOx = NO + NO2) recycling efficiency, dry deposition velocity, and RO2 + HO2 reaction rates. We focus our examination on the southeastern United States, which is impacted by both abundant isoprene emissions and high levels of anthropogenic pollutants. We find that NOx concentrations increase by 4–9% as a result of reduced removal by isoprene nitrate chemistry. O3 increases by 2 ppbv as a result of changes in NOx. OH concentrations increase by 30%, which can be primarily attributed to greater HOx production. We find that the model can capture observed total alkyl and multifunctional nitrates (∑ANs) and their relationship with O3 by assuming either an isoprene nitrate yield of 6% and daytime lifetime of 6 hours or a yield of 12% and lifetime of 4 h. Uncertainties in the isoprene nitrates can impact ozone production by 10% and OH concentrations by 6%. The uncertainties in NOx recycling efficiency appear to have larger effects than uncertainties in isoprene nitrate yield and dry deposition velocity. Further progress depends on improved understanding of isoprene oxidation pathways, the rate of NOx recycling from isoprene nitrates, and the fate of the secondary, tertiary, and further oxidation products of isoprene.
Turbulent collision-coalescence in maritime shallow convection

This paper discusses cloud simulations aiming at quantitative assessment of the effects of cloud turbulence on rain development in shallow ice-free convective clouds. Cloud fields from large-eddy simulations (LES) applying bin microphysics with the collection kernel enhanced by cloud turbulence are compared to those with the standard gravitational collection kernel. Simulations for a range of cloud condensation nuclei (CCN) concentrations are contrasted. Details on how the parameterized turbulent collection kernel is used in LES simulations are presented. Because of the disparity in spatial scales between the bottom-up numerical studies guiding the turbulent kernel development and the top-down LES simulations of cloud dynamics, we address the consequence of the turbulence intermittency in the unresolved range of scales on the mean collection kernel applied in LES. We show that intermittency effects are unlikely to play an important role in the current simulations. Highly-idealized single-cloud simulations are used to illustrate two mechanisms that operate in cloud field simulations. First, the microphysical enhancement leads to earlier formation of drizzle through faster autoconversion of cloud water into drizzle, as suggested by previous studies. Second, more efficient removal of condensed water from cloudy volumes when a turbulent collection kernel is used leads to an increased cloud buoyancy and enables clouds to reach higher levels. This is the dynamical enhancement. Both mechanisms operate in the cloud field simulations. The microphysical enhancement leads to the increased drizzle and rain inside clouds in simulations with high CCN. In low-CCN simulations with significant surface rainfall, dynamical enhancement leads to a larger contribution of deeper clouds to the entire cloud population, and results in a dramatically increased mean surface rain accumulation. These results call for future modeling and observational studies to corroborate the findings.
Investigating the influences of SO2 and NH3 levels on isoprene-derived secondary organic aerosol formation using conditional sampling approaches

Filter-based PM2.5 samples were chemically analyzed to investigate secondary organic aerosol (SOA) formation from isoprene in a rural atmosphere of the southeastern US influenced by both anthropogenic sulfur dioxide (SO2) and ammonia (NH3) emissions. Daytime PM2.5 samples were collected during summer 2010 using conditional sampling approaches based on pre-defined high and low SO2 or NH3 thresholds. Known molecular-level tracers for isoprene SOA formation, including 2-methylglyceric acid, 3-methyltetrahydrofuran-3,4-diols, 2-methyltetrols, C5-alkene triols, dimers, and organosulfate derivatives, were identified and quantified by gas chromatography coupled to electron ionization mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography coupled to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (UPLC/ESI-HR-Q-TOFMS). Mass concentrations of six isoprene low-NOx SOA tracers contributed to 12–19% of total organic matter (OM) in PM2.5 samples collected during the sampling period, indicating the importance of the hydroxyl radical (OH)-initiated oxidation (so-called photooxidation) of isoprene under low-NOx conditions that lead to SOA formation through reactive uptake of gaseous isoprene epoxydiols (IEPOX) in this region. The contribution of the IEPOX-derived SOA tracers to total organic matter was enhanced by 1.4% (p = 0.012) under high-SO2 sampling scenarios, although only weak associations between aerosol acidity and mass of IEPOX SOA tracers were observed. This suggests that IEPOX-derived SOA formation might be modulated by other factors simultaneously, rather than only aerosol acidity. No clear associations between isoprene SOA formation and high or low NH3 conditional samples were found. Positive correlations between sulfate aerosol loadings and IEPOX-derived SOA tracers for samples collected under all conditions indicates that sulfate aerosol could be a surrogate for surface accommodation in the uptake of IEPOX onto preexisting aerosols.
Analysis of a strong wildfire event over Valencia (Spain) during Summer 2012 – Part 1: Aerosol microphysics and optical properties

The most intense wildfire experienced in Eastern Spain since 2004 happened in Valencia during summer 2012. Although the fire was mostly active during days 29–30 June, a longer temporal period (from 24 June to 4 July) was selected for this analysis. Column-integrated, vertical resolved and surface aerosol observations were performed continuously at the Burjassot station throughout the studied period. The aerosol optical depth at 500 nm shows values larger than 2 for the most intense part of the wildfire and an extremely high maximum of 8 was detected on 29 June. The simultaneous increase of the Ångström exponent was also observed, indicating the important contribution of small particles in the smoke plume. An extraordinary increase in the particle concentration near the ground was observed and hence the measured scattering coefficient was drastically enhanced. The scattering coefficient and the PM2.5 level maxima reached the unusually high values of 2100 Mm−1 and 160 μg m−3, respectively. These records represent an enhancement factor of 26 and 7 with respect to the climatological averages found in this station during June and July. The surface maxima were observed with 1-day lag from the maximum AOD, and this fact is linked with the mixing layer amplitude and the sedimentation of smoke particles. The aerosol microphysical parameters and optical properties were determined for the whole period by combination of an inversion procedure and the Mie Theory. The smoke particles enhanced drastically the volume concentration of the fine mode with a maximum of 0.4 μm3 μm−2, which is 10 times higher than the climatological summer background in this site. The simultaneous presence of dust and smoke particles at different altitudes was observed and hence the coarse mode was also significant during the most intense period of the wildfire episode. Therefore the aerosol single scattering albedo and the asymmetry parameter obtained during the smoke cases display high variability which is partially modulated by the volume of coarse particles. The smoke episode highly contributed to increase the load of particles remaining in the atmosphere after the event, especially in the fine mode, although similar aerosol microphysical and optical properties were observed before and after the event. In addition, the particle concentration observed at surface level due to the wildfire episode largely contributes to exceed the EU annual limits for the particulate matter in the studied region.
The diurnal evolution of the urban heat island of Paris: a model-based case study during Summer 2006

The urban heat island (UHI) over Paris during summer 2006 was simulated using the Advanced Regional Prediction System (ARPS) updated with a simple urban parametrization at a horizontal resolution of 1 km. Two integrations were performed, one with the urban land cover of Paris and another in which Paris was replaced by cropland. The focus is on a five-day clear-sky period, for which the UHI intensity reaches its maximum. The diurnal evolution of the UHI intensity was found to be adequately simulated for this five day period. The maximum difference at night in 2 m temperature between urban and rural areas stemming from the urban heating is reproduced with a relative error of less than 10%. The UHI has an ellipsoidal shape and stretches along the prevailing wind direction. The maximum UHI intensity of 6.1 K occurs at 23:00 UTC located 6 km downstream of the city centre and this largely remains during the whole night. An idealized one-column model study demonstrates that the nocturnal differential sensible heat flux, even though much smaller than its daytime value, is mainly responsible for the maximum UHI intensity. The reason for this nighttime maximum is that additional heat is only affecting a shallow layer of 150 m. An air uplift is explained by the synoptic east wind and a ramp upwind of the city centre, which leads to a considerable nocturnal adiabatic cooling over cropland. The idealized study demonstrates that the reduced vertical adiabatic cooling over the city compared to cropland induces an additional UHI build-up of 25%. The UHI and its vertical extent is affected by the boundary-layer stability, nocturnal low-level jet as well as radiative cooling. Therefore, improvements of representing these boundary-layer features in atmospheric models are important for UHI studies.
Sources and photochemistry of volatile organic compounds in the remote atmosphere of western China: results from the Mt. Waliguan Observatory

The chemistry of the natural atmosphere and the influence by long-range transport of air pollution are key issues in the atmospheric sciences. Here we present two intensive field measurements of volatile organic compounds (VOCs) in late spring and summer of 2003 at Mt. Waliguan (WLG, 36.28° N, 100.90° E, 3816 m a.s.l.), a baseline station in the northeast part of the Qinghai-Tibetan Plateau. Most VOC species exhibited higher concentrations in late spring than in summer. A typical diurnal variation was observed with higher nighttime levels, in contrast to results from other mountainous sites. Five different air masses were identified from backward trajectory analysis showing distinct VOC speciation. Air masses originating from the central Eurasian continent contained the lowest VOC levels compared to the others that were impacted by anthropogenic emissions from China and the Indian subcontinent. A photochemical box model based on the Master Chemical Mechanism (version 3.2) and constrained by a full suite of measurements was developed to probe the photochemistry of atmosphere at WLG. Our results show net ozone production from in situ photochemistry during both late spring and summer. Oxidation of nitric oxide (NO) by the hydroperoxyl radical (HO2) dominates the ozone production relative to the oxidation by the organic peroxy radicals (RO2), and the ozone is primarily destroyed by photolysis and reactions with the HOx (HOx = OH + HO2) radicals. Ozone photolysis is the predominant primary source of radicals (ROx = OH + HO2 + RO2), followed by the photolysis of secondary oxygenated VOCs and hydrogen peroxides. The radical losses are governed by the self and cross reactions among the radicals. Overall, the findings of the present study provide insights into the background chemistry and the impacts of pollution transport on the pristine atmosphere over the Eurasian continent.
Re-analysis of ground-based microwave ClO measurements from Mauna Kea, 1992 to early 2012

We present a re-analysis of upper stratospheric ClO measurements from the ground-based millimeter-wave instrument from January 1992 to February 2012. These measurements are made as part of the Network for the Detection of Atmospheric Composition Change (NDACC) from Mauna Kea, Hawaii, (19.8° N, 204.5° E). Here, we use daytime and nighttime measurements together to form a day–night spectrum, from which the difference in the day and night profiles is retrieved. These results are then compared to the day–night difference profiles from the Upper Atmosphere Research Satellite (UARS) and Aura Microwave Limb Sounder (MLS) instruments. We also compare them to our previous analyses of the same data, in which we retrieved the daytime ClO profile. The major focus will be on comparing the year-to-year and long-term changes in ClO derived by the two analysis methods, and comparing these results to the long-term changes reported by others. We conclude that the re-analyzed data set has less short-term variability and exhibits a more constant long-term trend that is more consistent with other observations. Data from 1995 to 2012 indicate a linear decline of mid-stratospheric ClO of 0.64 ± 0.15% yr−1 (2σ).