ALBERT

Description: The concept of cloud radiative forcing (CRF) is commonly applied to quantify the impact of clouds on the surface radiative energy budget (REB). In the Arctic, specific radiative interactions between microphysical and macrophysical properties of clouds and the surface strongly modify the warming or cooling effect of clouds, complicating the estimate of CRF obtained from observations or models. Clouds tend to increase the broadband surface albedo over snow or sea ice surfaces compared to cloud-free conditions. However, this effect is not adequately considered in the derivation of CRF in the Arctic so far. Therefore, we have quantified the effects caused by surface-albedo–cloud interactions over highly reflective snow or sea ice surfaces on the CRF using radiative transfer simulations and below-cloud airborne observations above the heterogeneous springtime marginal sea ice zone (MIZ) during the Arctic CLoud Observations Using airborne measurements during polar Day (ACLOUD) campaign. The impact of a modified surface albedo in the presence of clouds, as compared to cloud-free conditions, and its dependence on cloud optical thickness is found to be relevant for the estimation of the shortwave CRF. A method is proposed to consider this surface albedo effect on CRF estimates by continuously retrieving the cloud-free surface albedo from observations under cloudy conditions, using an available snow and ice albedo parameterization. Using ACLOUD data reveals that the estimated average shortwave cooling by clouds almost doubles over snow- and ice-covered surfaces (−62 W m−2 instead of −32 W m−2), if surface-albedo–cloud interactions are considered. As a result, the observed total (shortwave plus longwave) CRF shifted from a warming effect to an almost neutral one. Concerning the seasonal cycle of the surface albedo, it is demonstrated that this effect enhances shortwave cooling in periods when snow dominates the surface and potentially weakens the cooling by optically thin clouds during the summertime melting season. These findings suggest that the surface-albedo–cloud interaction should be considered in global climate models and in long-term studies to obtain a realistic estimate of the shortwave CRF to quantify the role of clouds in Arctic amplification.

Description: Wetlands are the largest and most uncertain natural sources of atmospheric methane (CH4). Several process-based models have been developed to quantify the magnitude and estimate spatial and temporal variations in CH4 emissions from global wetlands. Reliable models are required to estimate global wetland CH4 emissions. This study aimed to test two process-based models, CH4MODwetland and Terrestrial Ecosystem Model (TEM), against the CH4 flux measurements of marsh, swamp, peatland and coastal wetland sites across the world; specifically, model accuracy and generality were evaluated for different wetland types and in different continents, and then the global CH4 emissions from 2000 to 2010 were estimated. Both models showed similar high correlations with the observed seasonal/annual total CH4 emissions, and the regression of the observed versus computed total seasonal/annual CH4 emissions resulted in R2 values of 0.81 and 0.68 for CH4MODwetland and TEM, respectively. The CH4MODwetland produced accurate predictions for marshes, peatlands, swamps and coastal wetlands, with model efficiency (EF) values of 0.22, 0.52, 0.13 and 0.72, respectively. TEM produced good predictions for peatlands and swamps, with EF values of 0.69 and 0.74, respectively, but it could not accurately simulate marshes and coastal wetlands (EF 

Description: As knowledge about the cirrus clouds in the lower stratosphere is limited, reliable long-term measurements are needed to assess their characteristics, radiative impact and important role in upper troposphere and lower stratosphere (UTLS) chemistry. We used 6 years (2006–2012) of Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) measurements to investigate the global and seasonal distribution of stratospheric cirrus clouds and compared the MIPAS results with results derived from the latest version (V4.x) of the Cloud-Aerosol Lidar and Infrared Pathfinder Satellite Observations (CALIPSO) data. For the identification of stratospheric cirrus clouds, precise information on both the cloud top height (CTH) and the tropopause height is crucial. Here, we used lapse rate tropopause heights estimated from the ERA-Interim global reanalysis. Considering the uncertainties of the tropopause heights and the vertical sampling grid, we define CTHs more than 0.5 km above the tropopause as stratospheric for CALIPSO data. For MIPAS data, we took into account the coarser vertical sampling grid and the broad field of view so that we considered cirrus CTHs detected more than 0.75 km above the tropopause as stratospheric. Further sensitivity tests were conducted to rule out sampling artefacts in MIPAS data. The global distribution of stratospheric cirrus clouds was derived from night-time measurements because of the higher detection sensitivity of CALIPSO. In both data sets, MIPAS and CALIPSO, the stratospheric cirrus cloud occurrence frequencies are significantly higher in the tropics than in the extra-tropics. Tropical hotspots of stratospheric cirrus clouds associated with deep convection are located over equatorial Africa, South and Southeast Asia, the western Pacific, and South America. Stratospheric cirrus clouds were more often detected in December–February (15 %) than June–August (8 %) in the tropics (±20∘). At northern and southern middle latitudes (40–60∘), MIPAS observed about twice as many stratospheric cirrus clouds (occurrence frequencies of 4 %–5 % for MIPAS rather than about 2 % for CALIPSO). We attribute more frequent observations of stratospheric cirrus clouds with MIPAS to the higher detection sensitivity of the instrument to optically thin clouds. In contrast to the difference between daytime and night-time occurrence frequencies of stratospheric cirrus clouds by a factor of about 2 in zonal means in the tropics (4 % and 10 %, respectively) and at middle latitudes for CALIPSO data, there is little diurnal cycle in MIPAS data, in which the difference of occurrence frequencies in the tropics is about 1 percentage point in zonal mean and about 0.5 percentage point at middle latitudes. The difference between CALIPSO day and night measurements can also be attributed to their differences in detection sensitivity. Future work should focus on better understanding the origin of the stratospheric cirrus clouds and their impact on radiative forcing and climate.

Description: Calculating a multi-model mean, a commonly used method for ensemble averaging, assumes model independence and equal model skill. Sharing of model components amongst families of models and research centres, conflated by growing ensemble size, means model independence cannot be assumed and is hard to quantify. We present a methodology to produce a weighted-model ensemble projection, accounting for model performance and model independence. Model weights are calculated by comparing model hindcasts to a selection of metrics chosen for their physical relevance to the process or phenomena of interest. This weighting methodology is applied to the Chemistry–Climate Model Initiative (CCMI) ensemble to investigate Antarctic ozone depletion and subsequent recovery. The weighted mean projects an ozone recovery to 1980 levels, by 2056 with a 95 % confidence interval (2052–2060), 4 years earlier than the most recent study. Perfect-model testing and out-of-sample testing validate the results and show a greater projective skill than a standard multi-model mean. Interestingly, the construction of a weighted mean also provides insight into model performance and dependence between the models. This weighting methodology is robust to both model and metric choices and therefore has potential applications throughout the climate and chemistry–climate modelling communities.

Description: Accurate reference spectroscopic information for the water molecule from the microwave to the near-ultraviolet is of paramount importance in atmospheric research. A semi-empirical potential energy surface for the ground electronic state of H216O has been created by refining almost 4000 experimentally determined energy levels. These states extend into regions with large values of rotational and vibrational excitation. For all states considered in our refinement procedure, which extend to 37 000 cm−1 and J=20 (total angular momentum), the average root-mean-square deviation is approximately 0.05 cm−1. This potential energy surface offers significant improvements when compared to recent models by accurately predicting states possessing high values of J. This feature will offer significant improvements in calculated line positions for high-temperature spectra where transitions between high J states become more prominent. Combining this potential with the latest dipole moment surface for water vapour, a line list has been calculated which extends reliably to 37 000 cm−1. Obtaining reliable results in the ultraviolet is of special importance as it is a challenging spectral region for the water molecule both experimentally and theoretically. Comparisons are made against several experimental sources of cross sections in the near-ultraviolet and discrepancies are observed. In the near-ultraviolet our calculations are in agreement with recent atmospheric retrievals and the upper limit obtained using broadband spectroscopy by Wilson et al. (2016, p. 194), but they do not support recent suggestions of very strong absorption in this region.

Description: North African dust reaches the southeastern United States every summer. Size-resolved dust mass measurements taken in Miami, Florida, indicate that more than one-half of the surface dust mass concentrations reside in particles with geometric diameters less than 2.1 µm, while vertical profiles of micropulse lidar depolarization ratios show dust reaching above 4 km during pronounced events. These observations are compared to the representation of dust in the Modern-Era Retrospective analysis for Research and Applications, version 2 (MERRA-2) aerosol reanalysis and closely related Goddard Earth Observing System model version 5 (GEOS-5) Forward Processing (FP) aerosol product, both of which assimilate satellite-derived aerosol optical depths using a similar protocol and inputs. These capture the day-to-day variability in aerosol optical depth well, in a comparison to an independent sun-photometer-derived aerosol optical depth dataset. Most of the modeled dust mass resides in diameters between 2 and 6 µm, in contrast to the measurements. Model-specified mass extinction efficiencies equate light extinction with approximately 3 times as much aerosol mass, in this size range, compared to the measured dust sizes. GEOS-5 FP surface-layer sea salt mass concentrations greatly exceed observed values, despite realistic winds and relative humidities. In combination, these observations help explain why, despite realistic total aerosol optical depths, (1) free-tropospheric model volume extinction coefficients are lower than those retrieved from the micro-pulse lidar, suggesting too-low model dust loadings in the free troposphere, and (2) model dust mass concentrations near the surface can be higher than those measured. The modeled vertical distribution of dust, when captured, is reasonable. Large, aspherical particles exceeding the modeled dust sizes are also occasionally present, but dust particles with diameters exceeding 10 µm contribute little to the measured total dust mass concentrations after such long-range transport. Remaining uncertainties warrant a further integrated assessment to confirm this study's interpretations.

Description: Marine boundary layer clouds, including the transition from stratocumulus to cumulus, are poorly represented in numerical weather prediction and general circulation models. Further uncertainties in the cloud structure arise in the presence of biomass burning carbonaceous aerosol, as is the case over the southeast Atlantic Ocean, where biomass burning aerosol is transported from the African continent. As the aerosol plume progresses across the southeast Atlantic Ocean, radiative heating within the aerosol layer has the potential to alter the thermodynamic environment and therefore the cloud structure; however, limited work has been done to quantify this along the trajectory of the aerosol plume in the region. The deployment of the first Atmospheric Radiation Measurement (ARM) Mobile Facility (AMF1) in support of the Layered Atlantic Smoke Interactions with Clouds field campaign provided a unique opportunity to collect observations of cloud and aerosol properties during two consecutive biomass burning seasons during July through October of 2016 and 2017 over Ascension Island (7.96∘ S, 14.35∘ W). Using observed profiles of temperature, humidity, and clouds from the field campaign alongside aerosol optical properties from Modern-Era Retrospective analysis for Research and Applications, Version 2 (MERRA-2), as input for the Rapid Radiation Transfer Model (RRTM), profiles of the radiative heating rate due to aerosols and clouds were computed. Radiative heating is also assessed across the southeast Atlantic Ocean using an ensemble of back trajectories from the Hybrid Single Particle Lagrangian Integrated Trajectory (HYSPLIT) model. Idealized experiments using the RRTM with and without aerosols and a range of values for the single-scattering albedo (SSA) demonstrate that shortwave (SW) heating within the aerosol layer above Ascension Island can locally range between 2 and 8 K d−1 depending on the aerosol optical properties, though impacts of the aerosol can be felt elsewhere in the atmospheric column. When considered under clear conditions, the aerosol has a cooling effect at the TOA, and based on the observed cloud properties at Ascension Island, the cloud albedo is not large enough to overcome this. Shortwave radiative heating due to biomass burning aerosol is not balanced by additional longwave (LW) cooling, and the net radiative impact results in a stabilization of the lower troposphere. However, these results are extremely sensitive to the single-scattering albedo assumptions in models.

Description: This paper addresses the question of how much uncertainties in CO2 fluxes over Australia can be reduced by assimilation of total-column carbon dioxide retrievals from the Orbiting Carbon Observatory-2 (OCO-2) satellite instrument. We apply a four-dimensional variational data assimilation system, based around the Community Multiscale Air Quality (CMAQ) transport-dispersion model. We ran a series of observing system simulation experiments to estimate posterior error statistics of optimized monthly-mean CO2 fluxes in Australia. Our assimilations were run with a horizontal grid resolution of 81 km using OCO-2 data for 2015. Based on four representative months, we find that the integrated flux uncertainty for Australia is reduced from 0.52 to 0.13 Pg C yr−1. Uncertainty reductions of up to 90 % were found at grid-point resolution over productive ecosystems. Our sensitivity experiments show that the choice of the correlation structure in the prior error covariance plays a large role in distributing information from the observations. We also found that biases in the observations would significantly impact the inverted fluxes and could contaminate the final results of the inversion. Biases in prior fluxes are generally removed by the inversion system. Biases in the boundary conditions have a significant impact on retrieved fluxes, but this can be mitigated by including boundary conditions in our retrieved parameters. In general, results from our idealized experiments suggest that flux inversions at this unusually fine scale will yield useful information on the carbon cycle at continental and finer scales.

Description: In order to track progress towards the global climate targets, the parties that signed the Paris Climate Agreement will regularly report their anthropogenic carbon dioxide (CO2) emissions based on energy statistics and CO2 emission factors. Independent evaluation of this self-reporting system is a fast-growing research topic. Here, we study the value of satellite observations of the column CO2 concentrations to estimate CO2 anthropogenic emissions with 5 years of the Orbiting Carbon Observatory-2 (OCO-2) retrievals over and around China. With the detailed information of emission source locations and the local wind, we successfully observe CO2 plumes from 46 cities and industrial regions over China and quantify their CO2 emissions from the OCO-2 observations, which add up to a total of 1.3 Gt CO2 yr−1 that accounts for approximately 13 % of mainland China's annual emissions. The number of cities whose emissions are constrained by OCO-2 here is 3 to 10 times larger than in previous studies that only focused on large cities and power plants in different locations around the world. Our satellite-based emission estimates are broadly consistent with the independent values from China's detailed emission inventory MEIC but are more different from those of two widely used global gridded emission datasets (i.e., EDGAR and ODIAC), especially for the emission estimates for the individual cities. These results demonstrate some skill in the satellite-based emission quantification for isolated source clusters with the OCO-2, despite the sparse sampling of this instrument not designed for this purpose. This skill can be improved by future satellite missions that will have a denser spatial sampling of surface emitting areas, which will come soon in the early 2020s.

Description: We develop a new large-scale hydrological and water resources model, the Community Water Model (CWatM), which can simulate hydrology both globally and regionally at different resolutions from 30 arcmin to 30 arcsec at daily time steps. CWatM is open source in the Python programming environment and has a modular structure. It uses global, freely available data in the netCDF4 file format for reading, storage, and production of data in a compact way. CWatM includes general surface and groundwater hydrological processes but also takes into account human activities, such as water use and reservoir regulation, by calculating water demands, water use, and return flows. Reservoirs and lakes are included in the model scheme. CWatM is used in the framework of the Inter-Sectoral Impact Model Intercomparison Project (ISIMIP), which compares global model outputs. The flexible model structure allows for dynamic interaction with hydro-economic and water quality models for the assessment and evaluation of water management options. Furthermore, the novelty of CWatM is its combination of state-of-the-art hydrological modeling, modular programming, an online user manual and automatic source code documentation, global and regional assessments at different spatial resolutions, and a potential community to add to, change, and expand the open-source project. CWatM also strives to build a community learning environment which is able to freely use an open-source hydrological model and flexible coupling possibilities to other sectoral models, such as energy and agriculture.

Description: Aerosol–cloud interactions are the largest source of uncertainty in quantifying anthropogenic radiative forcing. The large uncertainty is, in part, due to the difficulty of predicting cloud microphysical parameters, such as the cloud droplet number concentration (Nd). Even though rigorous first-principle approaches exist to calculate Nd, the cloud and aerosol research community also relies on empirical approaches such as relating Nd to aerosol mass concentration. Here we analyze relationships between Nd and cloud water chemical composition, in addition to the effect of environmental factors on the degree of the relationships. Warm, marine, stratocumulus clouds off the California coast were sampled throughout four summer campaigns between 2011 and 2016. A total of 385 cloud water samples were collected and analyzed for 80 chemical species. Single- and multispecies log–log linear regressions were performed to predict Nd using chemical composition. Single-species regressions reveal that the species that best predicts Nd is total sulfate (Radj2=0.40). Multispecies regressions reveal that adding more species does not necessarily produce a better model, as six or more species yield regressions that are statistically insignificant. A commonality among the multispecies regressions that produce the highest correlation with Nd was that most included sulfate (either total or non-sea-salt), an ocean emissions tracer (such as sodium), and an organic tracer (such as oxalate). Binning the data according to turbulence, smoke influence, and in-cloud height allowed for examination of the effect of these environmental factors on the composition–Nd correlation. Accounting for turbulence, quantified as the standard deviation of vertical wind speed, showed that the correlation between Nd with both total sulfate and sodium increased at higher turbulence conditions, consistent with turbulence promoting the mixing between ocean surface and cloud base. Considering the influence of smoke significantly improved the correlation with Nd for two biomass burning tracer species in the study region, specifically oxalate and iron. When binning by in-cloud height, non-sea-salt sulfate and sodium correlated best with Nd at cloud top, whereas iron and oxalate correlated best with Nd at cloud base.

Description: Landslides are the main source of sediment in most mountain ranges. Rivers then act as conveyor belts, evacuating landslide-derived sediment. Sediment dynamics are known to influence landscape evolution through interactions among landslide sediment delivery, fluvial transport and river incision into bedrock. Sediment delivery and its interaction with river incision therefore control the pace of landscape evolution and mediate relationships among tectonics, climate and erosion. Numerical landscape evolution models (LEMs) are well suited to study the interactions among these surface processes. They enable evaluation of a range of hypotheses at varying temporal and spatial scales. While many models have been used to study the dynamic interplay between tectonics, erosion and climate, the role of interactions between landslide-derived sediment and river incision has received much less attention. Here, we present HyLands, a hybrid landscape evolution model integrated within the TopoToolbox Landscape Evolution Model (TTLEM) framework. The hybrid nature of the model lies in its capacity to simulate both erosion and deposition at any place in the landscape due to fluvial bedrock incision, sediment transport, and rapid, stochastic mass wasting through landsliding. Fluvial sediment transport and bedrock incision are calculated using the recently developed Stream Power with Alluvium Conservation and Entrainment (SPACE) model. Therefore, rivers can dynamically transition from detachment-limited to transport-limited and from bedrock to bedrock–alluvial to fully alluviated states. Erosion and sediment production by landsliding are calculated using a Mohr–Coulomb stability analysis, while landslide-derived sediment is routed and deposited using a multiple-flow-direction, nonlinear deposition method. We describe and evaluate the HyLands 1.0 model using analytical solutions and observations. We first illustrate the functionality of HyLands to capture river dynamics ranging from detachment-limited to transport-limited conditions. Second, we apply the model to a portion of the Namche Barwa massif in eastern Tibet and compare simulated and observed landslide magnitude–frequency and area–volume scaling relationships. Finally, we illustrate the relevance of explicitly simulating landsliding and sediment dynamics over longer timescales for landscape evolution in general and river dynamics in particular. With HyLands we provide a new tool to understand both the long- and short-term coupling between stochastic hillslope processes, river incision and source-to-sink sediment dynamics.

Description: Chemistry plays an indispensable role in investigations of the atmosphere; however, many climate models either ignore or greatly simplify atmospheric chemistry, limiting both their accuracy and their scope. We present the development and evaluation of the online global atmospheric chemical model BCC-GEOS-Chem v1.0, coupling the GEOS-Chem chemical transport model (CTM) as an atmospheric chemistry component in the Beijing Climate Center atmospheric general circulation model (BCC-AGCM). The GEOS-Chem atmospheric chemistry component includes detailed tropospheric HOx–NOx–volatile organic compounds–ozone–bromine–aerosol chemistry and online dry and wet deposition schemes. We then demonstrate the new capabilities of BCC-GEOS-Chem v1.0 relative to the base BCC-AGCM model through a 3-year (2012–2014) simulation with anthropogenic emissions from the Community Emissions Data System (CEDS) used in the Coupled Model Intercomparison Project Phase 6 (CMIP6). The model captures well the spatial distributions and seasonal variations in tropospheric ozone, with seasonal mean biases of 0.4–2.2 ppbv at 700–400 hPa compared to satellite observations and within 10 ppbv at the surface to 500 hPa compared to global ozonesonde observations. The model has larger high-ozone biases over the tropics which we attribute to an overestimate of ozone chemical production. It underestimates ozone in the upper troposphere which is likely due either to the use of a simplified stratospheric ozone scheme or to biases in estimated stratosphere–troposphere exchange dynamics. The model diagnoses the global tropospheric ozone burden, OH concentration, and methane chemical lifetime to be 336 Tg, 1.16×106 molecule cm−3, and 8.3 years, respectively, which is consistent with recent multimodel assessments. The spatiotemporal distributions of NO2, CO, SO2, CH2O, and aerosol optical depth are generally in agreement with satellite observations. The development of BCC-GEOS-Chem v1.0 represents an important step for the development of fully coupled earth system models (ESMs) in China.

Description: We developed the WRF-GC model, an online coupling of the Weather Research and Forecasting (WRF) mesoscale meteorological model and the GEOS-Chem atmospheric chemistry model, for regional atmospheric chemistry and air quality modeling. WRF and GEOS-Chem are both open-source community models. WRF-GC offers regional modellers access to the latest GEOS-Chem chemical module, which is state of the science, well documented, traceable, benchmarked, actively developed by a large international user base, and centrally managed by a dedicated support team. At the same time, WRF-GC enables GEOS-Chem users to perform high-resolution forecasts and hindcasts for any region and time of interest. WRF-GC uses unmodified copies of WRF and GEOS-Chem from their respective sources; the coupling structure allows future versions of either one of the two parent models to be integrated into WRF-GC with relative ease. Within WRF-GC, the physical and chemical state variables are managed in distributed memory and translated between WRF and GEOS-Chem by the WRF-GC coupler at runtime. We used the WRF-GC model to simulate surface PM2.5 concentrations over China during 22 to 27 January 2015 and compared the results to surface observations and the outcomes from a GEOS-Chem Classic nested-China simulation. Both models were able to reproduce the observed spatiotemporal variations of regional PM2.5, but the WRF-GC model (r=0.68, bias =29 %) reproduced the observed daily PM2.5 concentrations over eastern China better than the GEOS-Chem Classic model did (r=0.72, bias =55 %). This was because the WRF-GC simulation, nudged with surface and upper-level meteorological observations, was able to better represent the pollution meteorology during the study period. The WRF-GC model is parallelized across computational cores and scales well on massively parallel architectures. In our tests where the two models were similarly configured, the WRF-GC simulation was 3 times more efficient than the GEOS-Chem Classic nested-grid simulation due to the efficient transport algorithm and the Message Passing Interface (MPI)-based parallelization provided by the WRF software framework. WRF-GC v1.0 supports one-way coupling only, using WRF-simulated meteorological fields to drive GEOS-Chem with no chemical feedbacks. The development of two-way coupling capabilities, i.e., the ability to simulate radiative and microphysical feedbacks of chemistry to meteorology, is under way. The WRF-GC model is open source and freely available from http://wrf.geos-chem.org (last access: 10 July 2020).

Description: Biomass burning emissions are a major source of trace gases and aerosols. Wildfires being highly variable in time and space, calculating emissions requires a numerical tool able to estimate fluxes at the kilometer scale and with an hourly time step. Here, the APIFLAME model version 2.0 is presented. It is structured to be modular in terms of input databases and processing methods. The main evolution compared to version 1.0 is the possibility of merging burned area and fire radiative power (FRP) satellite observations to modulate the temporal variations of fire emissions and to integrate small fires that may not be detected in the burned area product. Accounting for possible missed detection due to small fire results in an increase in burned area ranging from ∼5 % in Africa and Australia to ∼30 % in North America on average over the 2013–2017 time period based on the Moderate-Resolution Imaging Spectroradiometer (MODIS) Collection 6 fire products. An illustration for the case of southwestern Europe during the summer of 2016, marked by large wildfires in Portugal, is presented. Emissions calculated using different possible configurations of APIFLAME show a dispersion of 80 % on average over the domain during the largest wildfires (8–14 August 2016), which can be considered as an estimate of uncertainty of emissions. The main sources of uncertainty studied, by order of importance, are the emission factors, the calculation of the burned area, and the vegetation attribution. The aerosol (PM10) and carbon monoxide (CO) concentrations simulated with the CHIMERE regional chemistry transport model (CTM) are consistent with observations (good timing for the beginning and end of the events, ±1 d for the timing of the peak values) but tend to be overestimated compared to observations at surface stations. On the contrary, vertically integrated concentrations tend to be underestimated compared to satellite observations of total column CO by the Infrared Atmospheric Sounding Interferometer (IASI) instrument and aerosol optical depth (AOD) by MODIS. This underestimate is lower close to the fire region (5 %–40 % for AOD depending on the configuration and 8 %–18 % for total CO) but rapidly increases downwind. For all comparisons, better agreement is achieved when emissions are injected higher into the free troposphere using a vertical profile as estimated from observations of aerosol plume height by the Multi-angle Imaging SpectroRadiometer (MISR) satellite instrument (injection up to 4 km). Comparisons of aerosol layer heights to observations by the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) show that some parts of the plume may still be transported at too low an altitude. The comparisons of the different CTM simulations to observations point to uncertainties not only on emissions (total mass and daily variability) but also on the simulation of their transport with the CTM and mixing with other sources. Considering the uncertainty of the emission injection profile and of the modeling of the transport of these dense plumes, it is difficult to fully validate emissions through comparisons between model simulations and atmospheric observations.

Description: The aerosol mass spectrometer (AMS), combined with statistical methods such as positive matrix factorization (PMF), has greatly advanced the quantification of primary organic aerosol (POA) sources and total secondary organic aerosol (SOA) mass. However, the use of thermal vaporization and electron ionization yields extensive thermal decomposition and ionization-induced fragmentation, which limit chemical information needed for SOA source apportionment. The recently developed extractive electrospray ionization time-of-flight mass spectrometer (EESI-TOF) provides mass spectra of the organic aerosol fraction with a linear response to mass and no thermal decomposition or ionization-induced fragmentation. However, the costs and operational requirements of online instruments make their use impractical for long-term or spatially dense monitoring applications. This challenge was overcome for AMS measurements by measuring re-nebulized water extracts from ambient filter samples. Here, we apply the same strategy for EESI-TOF measurements of 1 year of 24 h filter samples collected approximately every fourth day throughout 2013 at an urban site. The nebulized water extracts were measured simultaneously with an AMS. The application of positive matrix factorization (PMF) to EESI-TOF spectra resolved seven factors, which describe water-soluble OA: less and more aged biomass burning aerosol (LABBEESI and MABBEESI, respectively), cigarette-smoke-related organic aerosol, primary biological organic aerosol, biogenic secondary organic aerosol, and a summer mixed oxygenated organic aerosol factor. Seasonal trends and relative contributions of the EESI-TOF OA sources were compared with AMS source apportionment factors, measured water-soluble ions, cellulose, and meteorological data. Cluster analysis was utilized to identify key factor-specific ions based on PMF. Both LABB and MABB contribute strongly during winter. LABB is distinguished by very high signals from C6H10O5 (levoglucosan and isomers) and C8H12O6, whereas MABB is characterized by a large number of CxHyOz and CxHyOzN species of two distinct populations: one with low H:C and high O:C and the other with high H:C and low O:C. Two oxygenated summertime SOA sources were attributed to terpene-derived biogenic SOA, a major summertime aerosol source in central Europe. Furthermore, a primary biological organic aerosol factor was identified, which was dominated by plant-derived fatty acids and correlated with free cellulose. The cigarette-smoke-related factor contained a high contribution of nicotine and high abundance of organic nitrate ions with low m∕z.

Description: Based on the fifth phase of the Coupled Model Intercomparison Project (CMIP5)-generation previous Institut Pierre Simon Laplace (IPSL) Earth system model, we designed a new version, IPSL-CM5A2, aiming at running multi-millennial simulations typical of deep-time paleoclimate studies. Three priorities were followed during the setup of the model: (1) improving the overall model computing performance, (2) overcoming a persistent cold bias depicted in the previous model generation and (3) making the model able to handle the specific continental configurations of the geological past. These developments include the integration of hybrid parallelization Message Passing Interface – Open Multi-Processing (MPI-OpenMP) in the atmospheric model of the Laboratoire de Météorologie Dynamique (LMDZ), the use of a new library to perform parallel asynchronous input/output by using computing cores as “I/O servers” and the use of a parallel coupling library between the ocean and the atmospheric components. The model, which runs with an atmospheric resolution of 3.75∘×1.875∘ and 2 to 0.5∘ in the ocean, can now simulate ∼100 years per day, opening new possibilities towards the production of multi-millennial simulations with a full Earth system model. The tuning strategy employed to overcome a persistent cold bias is detailed. The confrontation of a historical simulation to climatological observations shows overall improved ocean meridional overturning circulation, marine productivity and latitudinal position of zonal wind patterns. We also present the numerous steps required to run IPSL-CM5A2 for deep-time paleoclimates through a preliminary case study for the Cretaceous. Namely, specific work on the ocean model grid was required to run the model for specific continental configurations in which continents are relocated according to past paleogeographic reconstructions. By briefly discussing the spin-up of such a simulation, we elaborate on the requirements and challenges awaiting paleoclimate modeling in the next years, namely finding the best trade-off between the level of description of the processes and the computing cost on supercomputers.

Description: In a laboratory cloud chamber that is undergoing Rayleigh–Bénard convection, supersaturation is produced by isobaric mixing. When aerosols (cloud condensation nuclei) are injected into the chamber at a constant rate, and the rate of droplet activation is balanced by the rate of droplet loss, an equilibrium droplet size distribution (DSD) can be achieved. We derived analytic equilibrium DSDs and probability density functions (PDFs) of droplet radius and squared radius for conditions that could occur in such a turbulent cloud chamber when there is uniform supersaturation. We neglected the effects of droplet curvature and solute on the droplet growth rate. The loss rate due to fallout that we used assumes that (1) the droplets are well-mixed by turbulence, (2) when a droplet becomes sufficiently close to the lower boundary, the droplet's terminal velocity determines its probability of fallout per unit time, and (3) a droplet's terminal velocity follows Stokes' law (so it is proportional to its radius squared). Given the chamber height, the analytic PDF is determined by the mean supersaturation alone. From the expression for the PDF of the radius, we obtained analytic expressions for the first five moments of the radius, including moments for truncated DSDs. We used statistics from a set of measured DSDs to check for consistency with the analytic PDF. We found consistency between the theoretical and measured moments, but only when the truncation radius of the measured DSDs was taken into account. This consistency allows us to infer the mean supersaturations that would produce the measured PDFs in the absence of supersaturation fluctuations. We found that accounting for the truncation radius of the measured DSDs is particularly important when comparing the theoretical and measured relative dispersions of the droplet radius. We also included some additional quantities derived from the analytic DSD: droplet sedimentation flux, precipitation flux, and condensation rate.

Description: The aerosol-driven radiative effects on marine low-level cloud represent a large uncertainty in climate simulations, in particular over the Southern Ocean, which is also an important region for sea spray aerosol production. Observations of sea spray aerosol organic enrichment and the resulting impact on water uptake over the remote Southern Hemisphere are scarce, and therefore the region is under-represented in existing parameterisations. The Surface Ocean Aerosol Production (SOAP) voyage was a 23 d voyage which sampled three phytoplankton blooms in the highly productive water of the Chatham Rise, east of New Zealand. In this study we examined the enrichment of organics to nascent sea spray aerosol and the modifications to sea spray aerosol water uptake using in situ chamber measurements of seawater samples taken during the SOAP voyage. Primary marine organics contributed up to 23 % of the sea spray mass for particles with diameter less than approximately 1 µm and up to 79 % of the particle volume for 50 nm diameter sea spray. The composition of the submicron organic fraction was consistent throughout the voyage and was largely composed of a polysaccharide-like component, characterised by very low alkane-to-hydroxyl-concentration ratios of approximately 0.1–0.2. The enrichment of organics was compared to the output from the chlorophyll-a-based sea spray aerosol parameterisation suggested by Gantt et al. (2011) and the OCEANFILMS (Organic Compounds from Ecosystems to Aerosols: Natural Films and Interfaces via Langmuir Molecular Surfactants) models. OCEANFILMS improved on the representation of the organic fraction predicted using chlorophyll a, in particular when the co-adsorption of polysaccharides was included; however, the model still under-predicted the proportion of polysaccharides by an average of 33 %. Nascent 50 nm diameter sea spray aerosol hygroscopic growth factors measured at 90 % relative humidity averaged 1.93±0.08 and did not decrease with increasing sea spray aerosol organic fractions. The observed hygroscopicity was greater than expected from the assumption of full solubility, particularly during the most productive phytoplankton bloom (B1), during which organic fractions were greater than approximately 0.4. The water uptake behaviour observed in this study is consistent with that observed for other measurements of phytoplankton blooms and can be partially attributed to the presence of sea salt hydrates, which lowers the sea spray aerosol hygroscopicity when the organic enrichment is low. The inclusion of surface tension effects only marginally improved the modelled hygroscopicity, and a significant discrepancy between the observed and modelled hygroscopicity at high organic volume fractions remained. The findings from the SOAP voyage highlight the influence of biologically sourced organics on sea spray aerosol composition; these data improve the capacity to parameterise sea spray aerosol organic enrichment and water uptake.

Description: In the frame of the project “MOSAIK – Model-based city planning and application in climate change”, a German-wide research project within the call “Urban Climate Under Change” ([UC]2) funded by the German Federal Ministry of Education and Research (BMBF), a biometeorology module was implemented into the Parallelized Large-Eddy Simulation Model (PALM) system. The new biometeorology module is comprised of methods for the calculation of UV-exposure quantities, a human–biometeorologically weighted mean radiant temperature (Tmrt), as well as for the estimation of human thermal comfort or stress. The latter is achieved through the implementation of the three widely used thermal indices: perceived temperature (PT), Universal Thermal Climate Index (UTCI), as well as physiologically equivalent temperature (PET). Comparison calculations were performed for the PT, UTCI and PET indices based on the SkyHelios model and showing PALM calculates higher values in general. This is mostly due to a higher radiational gain leading to higher values of mean radiant temperature. For a more direct comparison, the PT, PET and UTCI indices were calculated by the biometeorology module, as well as the programs provided by the attachment to Verein Deutscher Ingenieure (VDI) guideline 3787, as well as by the RayMan model based on the very same input dataset. Results show deviations below the relevant precision of 0.1 K for PET and UTCI and some deviations of up to 2.683 K for PT caused by repeated unfavorable rounding in very rare cases (0.027 %).

Description: We examined recent atmospheric mercury concentrations measured with a high temporal resolution of 15 min at Mace Head, a GAW station on the western coast of Ireland. We attributed a direct contribution of 34 % (0.44 ng m−3) to primary sources. Additionally, a steep decline (0.05 ng yr−1) in mercury concentrations was observed between 2013 and 2018. Using a stereo algorithm we reconstructed 99.9 % of the atmospheric mercury. A conservative analysis demonstrated no decrease in total gaseous mercury (TGM) associated with atmospheric species typically used as tracers for oceanic emissions. The results show that the atmospheric mercury mass is mainly loaded in a baseline factor with an ongoing decline. Moreover, we exploit temporal variation and wind pattern effects in the measured atmospheric species; the results show that the diurnal variation and seasonality in TGM observed in Mace Head are closely related to other species linked to primary sources and can be explained by transport from continental areas.

Description: This study underlines the important role of the transported black carbon (BC) mass concentration in the West African monsoon (WAM) area. BC was measured with a micro-aethalometer integrated in the payload bay of the unmanned research aircraft ALADINA (Application of Light-weight Aircraft for Detecting IN situ Aerosol). As part of the DACCIWA (Dynamics–Aerosol–Chemistry–Cloud Interactions in West Africa) project, 53 measurement flights were carried out at Savè, Benin, on 2–16 July 2016. A high variability of BC (1.79 to 2.42±0.31 µg m−3) was calculated along 155 vertical profiles that were performed below cloud base in the atmospheric boundary layer (ABL). In contrast to initial expectations of primary emissions, the vertical distribution of BC was mainly influenced by the stratification of the ABL during the WAM season. The article focuses on an event (14 and 15 July 2016) which showed distinct layers of BC in the lowermost 900 m above ground level (a.g.l.). Low concentrations of NOx and CO were sampled at the Savè supersite near the aircraft measurements and suggested a marginal impact of local sources during the case study. The lack of primary BC emissions was verified by a comparison of the measured BC with the model COSMO-ART (Consortium for Small-scale Modelling–Aerosols and Reactive Trace gases) that was applied for the field campaign period. The modelled vertical profiles of BC led to the assumption that the measured BC was already altered, as the size was mainly dominated by the accumulation mode. Further, calculated vertical transects of wind speed and BC presume that the observed BC layer was transported from the south with maritime inflow but was mixed vertically after the onset of a nocturnal low-level jet at the measurement site. This report contributes to the scope of DACCIWA by linking airborne BC data with ground observations and a model, and it illustrates the importance of a more profound understanding of the interaction between BC and the ABL in the WAM region.

Description: Orographic wave clouds offer a natural laboratory to investigate cloud microphysical processes and their representation in atmospheric models. Wave clouds impact the larger-scale flow by the vertical redistribution of moisture and aerosol. Here we use detailed cloud microphysical observations from the Ice in Clouds Experiment – Layer Clouds (ICE-L) campaign to evaluate the recently developed Cloud Aerosol Interacting Microphysics (CASIM) module in the Met Office Unified Model (UM) with a particular focus on different parameterizations for heterogeneous freezing. Modelled and observed thermodynamic and microphysical properties agree very well (deviation of air temperature

Description: The complex and computationally expensive nature of landscape evolution models poses significant challenges to the inference and optimization of unknown model parameters. Bayesian inference provides a methodology for estimation and uncertainty quantification of unknown model parameters. In our previous work, we developed parallel tempering Bayeslands as a framework for parameter estimation and uncertainty quantification for the Badlands landscape evolution model. Parallel tempering Bayeslands features high-performance computing that can feature dozens of processing cores running in parallel to enhance computational efficiency. Nevertheless, the procedure remains computationally challenging since thousands of samples need to be drawn and evaluated. In large-scale landscape evolution problems, a single model evaluation can take from several minutes to hours and in some instances, even days or weeks. Surrogate-assisted optimization has been used for several computationally expensive engineering problems which motivate its use in optimization and inference of complex geoscientific models. The use of surrogate models can speed up parallel tempering Bayeslands by developing computationally inexpensive models to mimic expensive ones. In this paper, we apply surrogate-assisted parallel tempering where the surrogate mimics a landscape evolution model by estimating the likelihood function from the model. We employ a neural-network-based surrogate model that learns from the history of samples generated. The entire framework is developed in a parallel computing infrastructure to take advantage of parallelism. The results show that the proposed methodology is effective in lowering the computational cost significantly while retaining the quality of model predictions.

Description: The hygroscopic behavior of black carbon (BC)-containing particles (BCPs) has a significant impact on global and regional climate change. However, the mechanism and factors controlling the hygroscopicity of BCPs from different carbon sources are not well understood. Here, we systematically measured the equilibrium and kinetics of water uptake by 15 different BCPs (10 herb-derived BCPs, 2 wood-derived BCPs, and 3 soot-type BCPs) using a gravimetric water vapor sorption method combined with in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). In the gravimetric analysis, the sorption–desorption equilibrium isotherms were measured under continuous-stepwise water vapor pressure conditions, while the kinetics was measured at a variety of humidity levels obtained by different saturated aqueous salt solutions. The equilibrium water uptake of the tested group of BCPs at high relative humidity (〉80 %) positively correlated to the dissolved mineral content (0.01–13.0 wt %) (R2=0.86, P=0.0001), the content of the thermogravimetrically analyzed organic carbon (OCTGA, 4.48–15.25 wt %) (R2=0.52, P=0.002), and the content of the alkali-extracted organic carbon (OCAE, 0.14–8.39 wt %) (R2=0.80, P=0.0001). In contrast, no positive correlation was obtained with the content of total organic carbon or elemental carbon. Among the major soluble ionic constituents, chloride and ammonium were each correlated with the equilibrium water uptake at high relative humidity. Compared with the herbal BCPs and soot, the woody BCPs had much lower equilibrium water uptake, especially at high relative humidity, likely due to the very low dissolved mineral content and OC content. The DRIFTS analysis provided generally consistent results at low relative humidity. The kinetics of water uptake (measured by pseudo-second-order rate constant) correlated to the content of OCTGA and OCAE as well as the content of chloride and ammonium at low relative humidity (33 %) but to the porosity of BCPs at high relative humidity (94 %). This was the first study to show that BCPs of different types and sources had greatly varying hygroscopic properties.

Description: This paper describes the implementation of a coupling between a three-dimensional ocean general circulation model (NEMO) and a wave model (WW3) to represent the interactions of upper-oceanic flow dynamics with surface waves. The focus is on the impact of such coupling on upper-ocean properties (temperature and currents) and mixed layer depth (MLD) at global eddying scales. A generic coupling interface has been developed, and the NEMO governing equations and boundary conditions have been adapted to include wave-induced terms following the approach of McWilliams et al. (2004) and Ardhuin et al. (2008). In particular, the contributions of Stokes–Coriolis, vortex, and surface pressure forces have been implemented on top of the necessary modifications of the tracer–continuity equation and turbulent closure scheme (a one-equation turbulent kinetic energy – TKE – closure here). To assess the new developments, we perform a set of sensitivity experiments with a global oceanic configuration at 1/4∘ resolution coupled with a wave model configured at 1/2∘ resolution. Numerical simulations show a global increase in wind stress due to the interaction with waves (via the Charnock coefficient), particularly at high latitudes, resulting in increased surface currents. The modifications brought to the TKE closure scheme and the inclusion of a parameterization for Langmuir turbulence lead to a significant increase in the mixing, thus helping to deepen the MLD. This deepening is mainly located in the Southern Hemisphere and results in reduced sea surface currents and temperatures.

Description: Fires affect the composition of the atmosphere and Earth's radiation balance by emitting a suite of reactive gases and particles. An interactive fire module in an Earth system model (ESM) allows us to study the natural and anthropogenic drivers, feedbacks, and interactions of open fires. To do so, we have developed pyrE, the NASA GISS (Goddard Institute for Space Studies) interactive fire emissions module. The pyrE module is driven by environmental variables like flammability and cloud-to-ground lightning, calculated by the GISS ModelE ESM, and parameterized by anthropogenic impacts based on population density data. Fire emissions are generated from the flaming phase in pyrE (active fires). Using pyrE, we examine fire occurrence, regional fire suppression, burned area, fire emissions, and how it all affects atmospheric composition. To do so, we evaluate pyrE by comparing it to satellite-based datasets of fire count, burned area, fire emissions, and aerosol optical depth (AOD). We demonstrate pyrE's ability to simulate the daily and seasonal cycles of open fires and resulting emissions. Our results indicate that interactive fire emissions are biased low by 32 %–42 %, depending on emitted species, compared to the GFED4s (Global Fire Emissions Database) inventory. The bias in emissions drives underestimation in column densities, which is diluted by natural and anthropogenic emissions sources and production and loss mechanisms. Regionally, the resulting AOD of a simulation with interactive fire emissions is underestimated mostly over Indonesia compared to a simulation with GFED4s emissions and to MODIS AOD. In other parts of the world pyrE's performance in terms of AOD is marginal to a simulation with prescribed fire emissions.

Description: We present particle optical properties of stratospheric smoke layers observed with multiwavelength polarization Raman lidar over Punta Arenas (53.2∘ S, 70.9∘ W), Chile, at the southernmost tip of South America in January 2020. The smoke originated from the record-breaking bushfires in Australia. The stratospheric aerosol optical thickness reached values up to 0.85 at 532 nm in mid-January 2020. The main goal of this rapid communication letter is to provide first stratospheric measurements of smoke extinction-to-backscatter ratios (lidar ratios) and particle linear depolarization ratios at 355 and 532 nm wavelengths. These aerosol parameters are important input parameters in the analysis of spaceborne CALIPSO and Aeolus lidar observations of the Australian smoke spreading over large parts of the Southern Hemisphere in January and February 2020 up to heights of around 30 km. Lidar and depolarization ratios, simultaneously measured at 355 and 532 nm, are of key importance regarding the homogenization of the overall Aeolus (355 nm wavelength) and CALIPSO (532 nm wavelength) lidar data sets documenting the spread of the smoke and the decay of the stratospheric perturbation, which will be observable over the entire year of 2020. We found typical values and spectral dependencies of the lidar ratio and linear depolarization ratio for aged stratospheric smoke. At 355 nm, the lidar ratio and depolarization ratio ranged from 53 to 97 sr (mean 71 sr) and 0.2 to 0.26 (mean 0.23), respectively. At 532 nm, the lidar ratios were higher (75–112 sr, mean 97 sr) and the depolarization ratios were lower with values of 0.14–0.22 (mean 0.18). The determined depolarization ratios for aged Australian smoke are in very good agreement with respective ones for aged Canadian smoke, observed with lidar in stratospheric smoke layers over central Europe in the summer of 2017. The much higher 532 nm lidar ratios, however, indicate stronger absorption by the Australian smoke particles.

Description: The QA4ECV (Quality Assurance for Essential Climate Variables) version 1.1 stratospheric and tropospheric NO2 vertical column density (VCD) climate data records (CDRs) from the OMI (Ozone Monitoring Instrument) satellite sensor are validated using NDACC (Network for the Detection of Atmospheric Composition Change) zenith-scattered light differential optical absorption spectroscopy (ZSL-DOAS) and multi-axis DOAS (MAX-DOAS) data as a reference. The QA4ECV OMI stratospheric VCDs have a small bias of ∼0.2 Pmolec.cm-2 (5 %–10 %) and a dispersion of 0.2 to 1 Pmolec.cm-2 with respect to the ZSL-DOAS measurements. QA4ECV tropospheric VCD observations from OMI are restricted to near-cloud-free scenes, leading to a negative sampling bias (with respect to the unrestricted scene ensemble) of a few peta molecules per square centimetre (Pmolec.cm-2) up to −10 Pmolec.cm-2 (−40 %) in one extreme high-pollution case. The QA4ECV OMI tropospheric VCD has a negative bias with respect to the MAX-DOAS data (−1 to −4 Pmolec.cm-2), which is a feature also found for the OMI OMNO2 standard data product. The tropospheric VCD discrepancies between satellite measurements and ground-based data greatly exceed the combined measurement uncertainties. Depending on the site, part of the discrepancy can be attributed to a combination of comparison errors (notably horizontal smoothing difference error), measurement/retrieval errors related to clouds and aerosols, and the difference in vertical smoothing and a priori profile assumptions.

Description: The Observations for Model Intercomparison Project (Obs4MIPs) was initiated in 2010 to facilitate the use of observations in climate model evaluation and research, with a particular target being the Coupled Model Intercomparison Project (CMIP), a major initiative of the World Climate Research Programme (WCRP). To this end, Obs4MIPs (1) targets observed variables that can be compared to CMIP model variables; (2) utilizes dataset formatting specifications and metadata requirements closely aligned with CMIP model output; (3) provides brief technical documentation for each dataset, designed for nonexperts and tailored towards relevance for model evaluation, including information on uncertainty, dataset merits, and limitations; and (4) disseminates the data through the Earth System Grid Federation (ESGF) platforms, making the observations searchable and accessible via the same portals as the model output. Taken together, these characteristics of the organization and structure of obs4MIPs should entice a more diverse community of researchers to engage in the comparison of model output with observations and to contribute to a more comprehensive evaluation of the climate models. At present, the number of obs4MIPs datasets has grown to about 80; many are undergoing updates, with another 20 or so in preparation, and more than 100 are proposed and under consideration. A partial list of current global satellite-based datasets includes humidity and temperature profiles; a wide range of cloud and aerosol observations; ocean surface wind, temperature, height, and sea ice fraction; surface and top-of-atmosphere longwave and shortwave radiation; and ozone (O3), methane (CH4), and carbon dioxide (CO2) products. A partial list of proposed products expected to be useful in analyzing CMIP6 results includes the following: alternative products for the above quantities, additional products for ocean surface flux and chlorophyll products, a number of vegetation products (e.g., FAPAR, LAI, burned area fraction), ice sheet mass and height, carbon monoxide (CO), and nitrogen dioxide (NO2). While most existing obs4MIPs datasets consist of monthly-mean gridded data over the global domain, products with higher time resolution (e.g., daily) and/or regional products are now receiving more attention. Along with an increasing number of datasets, obs4MIPs has implemented a number of capability upgrades including (1) an updated obs4MIPs data specifications document that provides additional search facets and generally improves congruence with CMIP6 specifications for model datasets, (2) a set of six easily understood indicators that help guide users as to a dataset's maturity and suitability for application, and (3) an option to supply supplemental information about a dataset beyond what can be found in the standard metadata. With the maturation of the obs4MIPs framework, the dataset inclusion process, and the dataset formatting guidelines and resources, the scope of the observations being considered is expected to grow to include gridded in situ datasets as well as datasets with a regional focus, and the ultimate intent is to judiciously expand this scope to any observation dataset that has applicability for evaluation of the types of Earth system models used in CMIP.

Description: Ship emissions in and around ports are of interest for urban air quality management in many harbour cities. We investigated the impact of regional and local ship emissions on urban air quality for 2012 conditions in the city of Gothenburg, Sweden, the largest cargo port in Scandinavia. In order to assess the effects of ship emissions, a coupled regional- and local-scale model system has been set up using ship emissions in the Baltic Sea and the North Sea as well as in and around the port of Gothenburg. Ship emissions were calculated with the Ship Traffic Emission Assessment Model (STEAM), taking into account individual vessel characteristics and vessel activity data. The calculated contributions from local and regional shipping to local air pollution in Gothenburg were found to be substantial, especially in areas around the city ports. The relative contribution from local shipping to annual mean NO2 concentrations was 14 % as the model domain average, while the relative contribution from regional shipping in the North Sea and the Baltic Sea was 26 %. In an area close to the city terminals, the contribution of NO2 from local shipping (33 %) was higher than that of road traffic (28 %), which indicates the importance of controlling local shipping emissions. Local shipping emissions of NOx led to a decrease in the summer mean O3 levels in the city by 0.5 ppb (∼2 %) on average. Regional shipping led to a slight increase in O3 concentrations; however, the overall effect of regional and the local shipping together was a small decrease in the summer mean O3 concentrations in the city. In addition, volatile organic compound (VOC) emissions from local shipping compensate up to 4 ppb of the decrease in summer O3 concentrations due to the NO titration effect. For particulate matter with a median aerodynamic diameter less than or equal to 2.5 µm (PM2.5), local ship emissions contributed only 3 % to the annual mean in the model domain, while regional shipping under 2012 conditions was a larger contributor, with an annual mean contribution of 11 % of the city domain average. Based on the modelled local and regional shipping contributions, the health effects of PM2.5, NO2 and ozone were assessed using the ALPHA-RiskPoll (ARP) model. An effect of the shipping-associated PM2.5 exposure in the modelled area was a mean decrease in the life expectancy by 0.015 years per person. The relative contribution of local shipping to the impact of total PM2.5 was 2.2 %, which can be compared to the 5.3 % contribution from local road traffic. The relative contribution of the regional shipping was 10.3 %. The mortalities due to the exposure to NO2 associated with shipping were calculated to be 2.6 premature deaths yr−1. The relative contribution of local and regional shipping to the total exposure to NO2 in the reference simulation was 14 % and 21 %, respectively. The shipping-related ozone exposures were due to the NO titration effect leading to a negative number of premature deaths. Our study shows that overall health impacts of regional shipping can be more significant than those of local shipping, emphasizing that abatement policy options on city-scale air pollution require close cooperation across governance levels. Our findings indicate that the strengthened Sulphur Emission Control Areas (SECAs) fuel sulphur limit from 1 % to 0.1 % in 2015, leading to a strong decrease in the formation of secondary particulate matter on a regional scale was an important step in improving the air quality in the city.

Description: The Minamata Convention on Mercury (Hg) entered into force in 2017, committing its 116 parties (as of January 2019) to curb anthropogenic emissions. Monitoring of atmospheric concentrations and trends is an important part of the effectiveness evaluation of the convention. A few years ago (in 2017) we reported an increasing trend in atmospheric Hg concentrations at the Cape Point Global Atmosphere Watch (GAW) station in South Africa (34.3535∘ S, 18.4897∘ E) for the 2007–2015 period. With 2 more years of measurements at Cape Point and the 2012–2017 data from Amsterdam Island (37.7983∘ S, 77.5378∘ E) in the remote southern Indian Ocean, a more complex picture emerges: at Cape Point the upward trend for the 2007–2017 period is still significant, but no trend or a slightly downward trend was detected for the period 2012–2017 at both Cape Point and Amsterdam Island. The upward trend at Cape Point is driven mainly by the Hg concentration minimum in 2009 and maxima in 2014 and 2012. Using ancillary data on 222Rn, CO, O3, CO2, and CH4 from Cape Point and Amsterdam Island, the possible reasons for the trend and its change are investigated. In a companion paper this analysis is extended for the Cape Point station by calculations of source and sink regions using backward-trajectory analysis.

Description: The Chinese government has made many efforts to mitigate fine particulate matter pollution in recent years by taking strict measures on air pollutant reduction, which has generated the nationwide improvements in air quality since 2013. However, under the stringent air pollution controls, how the wintertime PM2.5 concentration (i.e., the mass concentration of atmospheric particles with diameters less than 2.5 µm) varies and how much the meteorological conditions contribute to the interannual variations in PM2.5 concentrations are still unclear, and these very important for the local government to assess the emission reduction of the previous year and adjust mitigation strategies for the next year. The effects of atmospheric circulation on the interannual variation in wintertime PM2.5 concentrations over the Beijing–Tianjin–Hebei (BTH) region in the period of 2013–2018 are evaluated in this study. Generally, the transport of clean and dry air masses and an unstable boundary layer in combination with the effective near-surface horizontal divergence or pumping action at the top of the boundary layer benefits the horizontal or vertical diffusion of surface air pollutants. Instead, the co-occurrence of a stable boundary layer, frequent air stagnation, positive water vapor advection and deep near-surface horizontal convergence exacerbate the wintertime air pollution. Favorable circulation conditions lasting for 2–4 d are beneficial for the diffusion of air pollutants, and 3–7 d of unfavorable circulation events exacerbates the accumulation of air pollutants. The occurrence frequency of favorable circulation events is consistent with the interannual variation in seasonal mean PM2.5 concentrations. There is better diffusion ability in the winters of 2014 and 2017 than in other years. A 59.9 % observed decrease in PM2.5 concentrations in 2017 over the BTH region could be attributed to the improvement in atmospheric diffusion conditions. It is essential to exclude the contribution of meteorological conditions to the variation in interannual air pollutants when making a quantitative evaluation of emission reduction measurements.

Description: This paper investigates the relative importance of turbulence and aerosol effects on the broadening of the droplet size distribution (DSD) during the early stage of cloud and raindrop formation. A parcel–DNS (direct numerical simulation) hybrid approach is developed to seamlessly simulate the evolution of cloud droplets in an ascending cloud parcel. The results show that turbulence and cloud condensation nuclei (CCN) hygroscopicity are key to the efficient formation of large droplets. The ultragiant aerosols can quickly form embryonic drizzle drops and thus determine the onset time of autoconversion. However, due to their scarcity in natural clouds, their contribution to the total mass of drizzle drops is insignificant. In the meantime, turbulence sustains the formation of large droplets by effectively accelerating the collisions of small droplets. The DSD broadening through turbulent collisions is significant and therefore yields a higher autoconversion rate compared to that in a nonturbulent case. It is argued that the level of autoconversion is heavily determined by turbulence intensity. This paper also presents an in-cloud seeding scenario designed to scrutinize the effect of aerosols in terms of number concentration and size. It is found that seeding more aerosols leads to higher competition for water vapor, reduces the mean droplet radius, and therefore slows down the autoconversion rate. On the other hand, increasing the seeding particle size can buffer such a negative feedback. Despite the fact that the autoconversion rate is prominently altered by turbulence and seeding, bulk variables such as liquid water content (LWC) stays nearly identical among all cases. Additionally, the lowest autoconversion rate is not co-located with the smallest mean droplet radius. The finding indicates that the traditional Kessler-type or Sundqvist-type autoconversion parameterizations, which depend on the LWC or mean radius, cannot capture the drizzle formation process very well. Properties related to the width or the shape of the DSD are also needed, suggesting that the scheme of Berry and Reinhardt (1974) is conceptually better. It is also suggested that a turbulence-dependent relative-dispersion parameter should be considered.

Description: The GEOS-Chem simulation of atmospheric CH4 was evaluated against observations from the Thermal and Near Infrared Sensor for Carbon Observations Fourier Transform Spectrometer (TANSO-FTS) on the Greenhouse Gases Observing Satellite (GOSAT), the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS), and the Total Carbon Column Observing Network (TCCON). We focused on the model simulations at the 4∘×5∘ and 2∘×2.5∘ horizontal resolutions for the period of February–May 2010. Compared to the GOSAT, TCCON, and ACE-FTS data, we found that the 2∘×2.5∘ model produced a better simulation of CH4, with smaller biases and a higher correlation to the independent data. We found large resolution-dependent differences such as a latitude-dependent XCH4 bias, with higher column abundances of CH4 at high latitudes and lower abundances at low latitudes at the 4∘×5∘ resolution than at 2∘×2.5∘. We also found large differences in CH4 column abundances between the two resolutions over major source regions such as China. These differences resulted in up to 30 % differences in inferred regional CH4 emission estimates from the two model resolutions. We performed several experiments using 222Rn, 7Be, and CH4 to determine the origins of the resolution-dependent errors. The results suggested that the major source of the latitude-dependent errors is excessive mixing in the upper troposphere and lower stratosphere, including mixing at the edge of the polar vortex, which is pronounced at the 4∘×5∘ resolution. At the coarser resolution, there is weakened vertical transport in the troposphere at midlatitudes to high latitudes due to the loss of sub-grid tracer eddy mass flux in the storm track regions. The vertical air mass fluxes are calculated in the model from the degraded coarse-resolution wind fields and the model does not conserve the air mass flux between model resolutions; as a result, the low resolution does not fully capture the vertical transport. This produces significant localized discrepancies, such as much greater CH4 abundances in the lower troposphere over China at 4∘×5∘ than at 2∘×2.5∘. Although we found that the CH4 simulation is significantly better at 2∘×2.5∘ than at 4∘×5∘, biases may still be present at 2∘×2.5∘ resolution. Their importance, particularly in regards to inverse modeling of CH4 emissions, should be evaluated in future studies using online transport in the native general circulation model as a benchmark simulation.

Description: Isoprene-derived secondary organic aerosol (iSOA) is a significant contributor to organic carbon (OC) in some forested regions, such as tropical rainforests and the Southeastern US. However, its contribution to organic aerosol in urban areas that have high levels of anthropogenic pollutants is poorly understood. In this study, we examined the formation of anthropogenically influenced iSOA during summer in Beijing, China. Local isoprene emissions and high levels of anthropogenic pollutants, in particular NOx and particulate SO42-, led to the formation of iSOA under both high- and low-NO oxidation conditions, with significant heterogeneous transformations of isoprene-derived oxidation products to particulate organosulfates (OSs) and nitrooxy-organosulfates (NOSs). Ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was combined with a rapid automated data processing technique to quantify 31 proposed iSOA tracers in offline PM2.5 filter extracts. The co-elution of the inorganic ions in the extracts caused matrix effects that impacted two authentic standards differently. The average concentration of iSOA OSs and NOSs was 82.5 ng m−3, which was around 3 times higher than the observed concentrations of their oxygenated precursors (2-methyltetrols and 2-methylglyceric acid). OS formation was dependant on both photochemistry and the sulfate available for reactive uptake, as shown by a strong correlation with the product of ozone (O3) and particulate sulfate (SO42-). A greater proportion of high-NO OS products were observed in Beijing compared with previous studies in less polluted environments. The iSOA-derived OSs and NOSs represented 0.62 % of the oxidized organic aerosol measured by aerosol mass spectrometry on average, but this increased to ∼3 % on certain days. These results indicate for the first time that iSOA formation in urban Beijing is strongly controlled by anthropogenic emissions and results in extensive conversion to OS products from heterogenous reactions.

Description: High-time-resolution measurements of in situ aerosol and cloud properties provide the ability to study regional atmospheric processes that occur on timescales of minutes to hours. However, one limitation to this approach is that continuous measurements often include periods when the data collected are not representative of the regional aerosol. Even at remote locations, submicron aerosols are pervasive in the ambient atmosphere with many sources. Therefore, periods dominated by local aerosol should be identified before conducting subsequent analyses to understand aerosol regional processes and aerosol–cloud interactions. Here, we present a novel method to validate the identification of regional baseline aerosol data by applying a mathematical algorithm to the data collected at the U.S. Department of Energy's (DOE) Atmospheric Radiation Measurement (ARM) user facility in the eastern North Atlantic (ENA). The ENA central facility (C1) includes an aerosol observing system (AOS) for the measurement of aerosol physical, optical, and chemical properties at time resolutions from seconds to minutes. A second temporary supplementary facility (S1), located ∼0.75 km from C1, was deployed for ∼1 year during the Aerosol and Cloud Experiments (ACE-ENA) campaign in 2017. First, we investigate the local aerosol at both locations. We associate periods of high submicron number concentration (Ntot) in the fine-mode condensation particle counter (CPC) and size distributions from the Ultra-High Sensitivity Aerosol Spectrometer (UHSAS) as a function of wind direction using a meteorology sensor with local sources. Elevated concentrations of Aitken-mode (

Description: Wet processes, including aqueous-phase chemistry, wet scavenging, and wet surface uptake during dry deposition, are important for global modeling of aerosols and aerosol precursors. In this study, we improve the treatments of these wet processes in the Goddard Earth Observing System with chemistry (GEOS-Chem) v12.6.0, including pH calculations for cloud, rain, and wet surfaces, the fraction of cloud available for aqueous-phase chemistry, rainout efficiencies for various types of clouds, empirical washout by rain and snow, and wet surface uptake during dry deposition. We compare simulated surface mass concentrations of aerosols and aerosol precursors with surface monitoring networks over the United States, European, Asian, and Arctic regions, and show that model results with updated wet processes agree better with measurements for most species. With the implementation of these updates, normalized mean biases (NMBs) of surface nitric acid, nitrate, and ammonium are reduced from 78 %, 126 %, and 45 % to 0.9 %, 15 %, and 4.1 % over the US sites, from 107 %, 127 %, and 90 % to −0.7 %, 4.2 %, and 16 % over European sites, and from 121 %, 269 %, and 167 % to −21 %, 37 %, and 86 % over Asian remote region sites. Comparison with surface measured SO2, sulfate, and black carbon at four Arctic sites indicated that those species simulated with the updated wet processes match well with observations except for a large underestimate of black carbon at one of the sites. We also compare our model simulation with aircraft measurement of nitric acid and aerosols during the Atmospheric Tomography Mission (ATom)-1 and ATom-2 periods and found a significant improvement of modeling skill of nitric acid, sulfate, and ammonium in the Northern Hemisphere during wintertime. The NMBs of these species are reduced from 163 %, 78 %, and 217 % to −13 %, −1 %, and 10 %, respectively. The investigation of impacts of updated wet process treatments on surface mass concentrations indicated that the updated wet processes have strong impacts on the global means of nitric acid, sulfate, nitrate, and ammonium and relative small impacts on the global means of sulfur dioxide, dust, sea salt, black carbon, and organic carbon.

Description: Haze pollution is affected by local air pollutants, regional transport of background particles and precursors, atmospheric chemistry related to secondary aerosol formation, and meteorological conditions conducive to physical, dynamical, and chemical processes. In the large, populated and industrialized areas like the Asian continental outflow region, the combination of regional transport and local stagnation often exacerbates urban haze pollution. However, the detailed chemical processes underlying the enhancement of urban haze induced by the combined effect of local emissions and transported remote pollutants are still unclear. Here, we demonstrate an important role of transported hygroscopic particles in increasing local inorganic aerosols, by studying the chemical composition of PM2.5 collected between October 2012 and June 2014 in Seoul, a South Korean megacity in the Asian continental outflow region, using the ISORROPIA II thermodynamic model. PM2.5 measured under the condition of regional transport from the upwind source areas in China was higher in mass concentration and richer in secondary inorganic aerosol (SIA) species (SO42-, NO3-, and NH4+) and aerosol liquid water (ALW) compared to that measured under non-transport conditions. The secondary inorganic species and ALW were both increased, particularly in cases with high PM2.5 levels, and this indicates inorganic species as a major driver of hygroscopicity. We conclude that the urban haze pollution in a continental outflow region like Seoul, particularly during the cold season, can be exacerbated by ALW in the transported particles, which enhances the nitrate partitioning into the particle phase in NOx- and NH3-rich urban areas. This study reveals the synergistic effect of remote and local sources on urban haze pollution in the downwind region and provides insight into the nonlinearity of domestic and foreign contributions to receptor PM2.5 concentrations in numerical air quality models.

Description: We present the development of a multiphase adjoint for the Community Multiscale Air Quality (CMAQ) model, a widely used chemical transport model. The adjoint model provides location- and time-specific gradients that can be used in various applications such as backward sensitivity analysis, source attribution, optimal pollution control, data assimilation, and inverse modeling. The science processes of the CMAQ model include gas-phase chemistry, aerosol dynamics and thermodynamics, cloud chemistry and dynamics, diffusion, and advection. Discrete adjoints are implemented for all the science processes, with an additional continuous adjoint for advection. The development of discrete adjoints is assisted with algorithmic differentiation (AD) tools. Particularly, the Kinetic PreProcessor (KPP) is implemented for gas-phase and aqueous chemistry, and two different automatic differentiation tools are used for other processes such as clouds, aerosols, diffusion, and advection. The continuous adjoint of advection is developed manually. For adjoint validation, the brute-force or finite-difference method (FDM) is implemented process by process with box- or column-model simulations. Due to the inherent limitations of the FDM caused by numerical round-off errors, the complex variable method (CVM) is adopted where necessary. The adjoint model often shows better agreement with the CVM than with the FDM. The adjoints of all science processes compare favorably with the FDM and CVM. In an example application of the full multiphase adjoint model, we provide the first estimates of how emissions of particulate matter (PM2.5) affect public health across the US.

Description: The present generation of global climate models is characterised by insufficient reflection of short-wave radiation over the Southern Ocean due to a misrepresentation of clouds. This is a significant concern as it leads to excessive heating of the ocean surface, sea surface temperature biases and subsequent problems with atmospheric dynamics. In this study, we modify cloud microphysics in a recent version of the Met Office's Unified Model and show that choosing a more realistic value for the shape parameter of atmospheric ice crystals, in better agreement with theory and observations, benefits the simulation of short-wave radiation. In the model, for calculating the growth rate of ice crystals through deposition, the default assumption is that all ice particles are spherical in shape. We modify this assumption to effectively allow for oblique shapes or aggregates of ice crystals. Along with modified ice nucleation temperatures, we achieve a reduction in the annual-mean short-wave cloud radiative effect over the Southern Ocean by up to ∼4 W m−2 and seasonally much larger reductions compared to the control model. By slowing the growth of the ice phase, the model simulates substantially more supercooled liquid cloud.

Description: Regional-scale chemistry-transport models have coarse spatial resolution (coarser than 1 km ×1 km) and can thus only simulate background concentrations. They fail to simulate the high concentrations observed close to roads and in streets, where a large part of the urban population lives. Local-scale models may be used to simulate concentrations in streets. They often assume that background concentrations are constant and/or use simplified chemistry. Recently developed, the multi-scale model Street-in-Grid (SinG) estimates gaseous pollutant concentrations simultaneously at local and regional scales by coupling them dynamically. This coupling combines the regional-scale chemistry-transport model Polair3D and a street-network model, the Model of Urban Network of Intersecting Canyons and Highway (MUNICH), with a two-way feedback. MUNICH explicitly models street canyons and intersections, and it is coupled to the first vertical level of the chemical-transport model, enabling the transfer of pollutant mass between the street-canyon roof and the atmosphere. The original versions of SinG and MUNICH adopt a stationary hypothesis to estimate pollutant concentrations in streets. Although the computation of the NOx concentration is numerically stable with the stationary approach, the partitioning between NO and NO2 is highly dependent on the time step of coupling between transport and chemistry processes. In this study, a new nonstationary approach is presented with a fine coupling between transport and chemistry, leading to numerically stable partitioning between NO and NO2. Simulations of NO, NO2 and NOx concentrations over Paris with SinG, MUNICH and Polair3D are compared to observations at traffic and urban stations to estimate the added value of multi-scale modeling with a two-way dynamical coupling between the regional and local scales. As expected, the regional chemical-transport model underestimates NO and NO2 concentrations in the streets. However, there is good agreement between the measurements and the concentrations simulated with MUNICH and SinG. The two-way dynamic coupling between the local and regional scales tends to be important for streets with an intermediate aspect ratio and with high traffic emissions.

Description: The measurements of aerosol particles with a filter inlet for gases and aerosols (FIGAERO) together with a chemical ionisation mass spectrometer (CIMS) yield the overall chemical composition of the particle phase. In addition, the thermal desorption profiles obtained for each detected ion composition contain information about the volatility of the detected compounds, which is an important property for understanding many physical properties like gas–particle partitioning. We coupled this thermal desorption method with isothermal evaporation prior to the sample collection to investigate the chemical composition changes during isothermal particle evaporation and particulate-water-driven chemical reactions in α-pinene secondary organic aerosol (SOA) of three different oxidative states. The thermal desorption profiles of all detected elemental compositions were then analysed with positive matrix factorisation (PMF) to identify the drivers of the chemical composition changes observed during isothermal evaporation. The keys to this analysis were to use the error matrix as a tool to weight the parts of the data carrying most information (i.e. the peak area of each thermogram) and to run PMF on a combined data set of multiple thermograms from different experiments to enable a direct comparison of the individual factors between separate measurements. The PMF was able to identify instrument background factors and separate them from the part of the data containing particle desorption information. Additionally, PMF allowed us to separate the direct desorption of compounds detected at a specific elemental composition from other signals with the same composition that stem from the thermal decomposition of thermally instable compounds with lower volatility. For each SOA type, 7–9 factors were needed to explain the observed thermogram behaviour. The contribution of the factors depended on the prior isothermal evaporation. Decreased contributions from the factors with the lowest desorption temperatures were observed with increasing isothermal evaporation time. Thus, the factors identified by PMF could be interpreted as volatility classes. The composition changes in the particles due to isothermal evaporation could be attributed to the removal of volatile factors with very little change in the desorption profiles of the individual factors (i.e. in the respective temperatures of peak desorption, Tmax). When aqueous-phase reactions took place, PMF was able to identify a new factor that directly identified the ions affected by the chemical processes. We conducted a PMF analysis of the FIGAERO–CIMS thermal desorption data for the first time using laboratory-generated SOA particles. But this method can be applied to, for example, ambient FIGAERO–CIMS measurements as well. There, the PMF analysis of the thermal desorption data identifies organic aerosol (OA) sources (such as biomass burning or oxidation of different precursors) and types, e.g. hydrocarbon-like (HOA) or oxygenated organic aerosol (OOA). This information could also be obtained with the traditional approach, namely the PMF analysis of the mass spectra data integrated for each thermogram. But only our method can also obtain the volatility information for each OA source and type. Additionally, we can identify the contribution of thermal decomposition to the overall signal.

Description: The global oxidation capacity, defined as the tropospheric mean concentration of the hydroxyl radical (OH), controls the lifetime of reactive trace gases in the atmosphere such as methane and carbon monoxide (CO). Models tend to underestimate the methane lifetime and CO concentrations throughout the troposphere, which is consistent with excessive OH. Approximately half of the oxidation of methane and non-methane volatile organic compounds (VOCs) is thought to occur over the oceans where oxidant chemistry has received little validation due to a lack of observational constraints. We use observations from the first two deployments of the NASA ATom aircraft campaign during July–August 2016 and January–February 2017 to evaluate the oxidation capacity over the remote oceans and its representation by the GEOS-Chem chemical transport model. The model successfully simulates the magnitude and vertical profile of remote OH within the measurement uncertainties. Comparisons against the drivers of OH production (water vapor, ozone, and NOy concentrations, ozone photolysis frequencies) also show minimal bias, with the exception of wintertime NOy. The severe model overestimate of NOy during this period may indicate insufficient wet scavenging and/or missing loss on sea-salt aerosols. Large uncertainties in these processes require further study to improve simulated NOy partitioning and removal in the troposphere, but preliminary tests suggest that their overall impact could marginally reduce the model bias in tropospheric OH. During the ATom-1 deployment, OH reactivity (OHR) below 3 km is significantly enhanced, and this is not captured by the sum of its measured components (cOHRobs) or by the model (cOHRmod). This enhancement could suggest missing reactive VOCs but cannot be explained by a comprehensive simulation of both biotic and abiotic ocean sources of VOCs. Additional sources of VOC reactivity in this region are difficult to reconcile with the full suite of ATom measurement constraints. The model generally reproduces the magnitude and seasonality of cOHRobs but underestimates the contribution of oxygenated VOCs, mainly acetaldehyde, which is severely underestimated throughout the troposphere despite its calculated lifetime of less than a day. Missing model acetaldehyde in previous studies was attributed to measurement uncertainties that have been largely resolved. Observations of peroxyacetic acid (PAA) provide new support for remote levels of acetaldehyde. The underestimate in both model acetaldehyde and PAA is present throughout the year in both hemispheres and peaks during Northern Hemisphere summer. The addition of ocean sources of VOCs in the model increases cOHRmod by 3 % to 9 % and improves model–measurement agreement for acetaldehyde, particularly in winter, but cannot resolve the model summertime bias. Doing so would require 100 Tg yr−1 of a long-lived unknown precursor throughout the year with significant additional emissions in the Northern Hemisphere summer. Improving the model bias for remote acetaldehyde and PAA is unlikely to fully resolve previously reported model global biases in OH and methane lifetime, suggesting that future work should examine the sources and sinks of OH over land.

Description: Anthropogenic aerosols impact cirrus clouds through ice nucleation, thereby changing the Earth's radiation budget. However, the magnitude and sign of anthropogenic forcing in cirrus clouds is still very uncertain depending on the treatments for ice-nucleating particles (INPs), the treatments for haze particle freezing, and the ice nucleation scheme. In this study, a new ice nucleation scheme (hereafter the HYBRID scheme) is developed to combine the best features of two previous ice nucleation schemes, so that global models are able to calculate the ice number concentration in both updrafts and downdrafts associated with gravity waves, and it has a robust sensitivity to the change of aerosol number. The scheme is applied in a box model, and the ice number concentrations (9.52±2.08 L−1) are somewhat overestimated but are in reasonable agreement with those from an adiabatic parcel model (9.40±2.31 L−1). Then, the forcing and cloud changes associated with changes in aircraft soot, sulfur emission, and all anthropogenic emissions between the preindustrial (PI) period and the present day (PD) are examined using the CESM/IMPACT global model with the HYBRID scheme. Aircraft soot emissions decrease the global average ice number concentration (Ni) by -1.0±2.4×107 m−2 (−1 %) (over the entire column) due to the inhibition of homogeneous nucleation and lead to a radiative forcing of -0.14±0.07 W m−2, while the increase in sulfur emissions increases the global average Ni by 7.3±2.9×107 m−2 (5 %) due to the increase in homogeneous nucleation and leads to a radiative forcing of -0.02±0.06 W m−2. The possible effects of aerosol and cloud feedbacks to the meteorological state in remote regions partly contribute to reduce the forcing and the change in Ni due to anthropogenic emissions. The radiative forcing due to all increased anthropogenic emissions from PI to PD is estimated to be -0.20±0.05 W m−2. If newly formed secondary organic aerosols (SOAs) act as INPs and inhibit homogeneous nucleation, the Ni formed from heterogeneous nucleation is increased. As a result, the inclusion of INPs from SOA increases the change in Ni to 12.0±2.3×107 m−2 (9 %) and increases (makes less negative) the anthropogenic forcing on cirrus clouds to -0.04±0.08 W m−2 from PI to PD.

Description: Land transport is an important emission source of nitrogen oxides, carbon monoxide, and volatile organic compounds. The emissions of nitrogen oxides affect air quality directly. Further, all of these emissions serve as a precursor for the formation of tropospheric ozone, thus leading to an indirect influence on air quality. In addition, ozone is radiatively active and its increase leads to a positive radiative forcing. Due to the strong non-linearity of the ozone chemistry, the contribution of emission sources to ozone cannot be calculated or measured directly. Instead, atmospheric chemistry models equipped with specific source attribution methods (e.g. tagging methods) are required. In this study we investigate the contribution of land transport emissions to ozone and ozone precursors using the MECO(n) model system (MESSy-fied ECHAM and COSMO models nested n times). This model system couples a global and a regional chemistry climate model and is equipped with a tagging diagnostic. We investigate the combined effect of long-range-transported ozone and ozone which is produced by European emissions by applying the tagging diagnostic simultaneously and consistently on the global and regional scale. We performed two simulations each covering 3 years with different anthropogenic emission inventories for Europe. We applied two regional refinements, i.e. one refinement covering Europe (50 km resolution) and one covering Germany (12 km resolution). The diagnosed absolute contributions of land transport emissions to reactive nitrogen (NOy) near ground level are in the range of 5 to 10 nmol mol−1. This corresponds to relative contributions of 50 % to 70 %. The largest absolute contributions appear around Paris, southern England, Moscow, the Po Valley, and western Germany. The absolute contributions to carbon monoxide range from 30 nmol mol−1 to more than 75 nmol mol−1 near emission hot-spots such as Paris or Moscow. The ozone which is attributed to land transport emissions shows a strong seasonal cycle with absolute contributions of 3 nmol mol−1 during winter and 5 to 10 nmol mol−1 during summer. This corresponds to relative contributions of 8 % to 10 % during winter and up to 16 % during summer. The largest values during summer are confined to the Po Valley, while the contributions in western Europe range from 12 % to 14 %. Only during summer are the ozone contributions slightly influenced by the anthropogenic emission inventory, but these differences are smaller than the range of the seasonal cycle of the contribution to land transport emissions. This cycle is caused by a complex interplay of seasonal cycles of other emissions (e.g. biogenic) and seasonal variations of the ozone regimes. In addition, our results suggest that during events with large ozone values the ozone contributions of land transport and biogenic emissions increase strongly. Here, the contribution of land transport emissions peaks up to 28 %. Hence, our model results suggest that land transport emissions are an important contributor during periods with large ozone values.

Description: The Earth's equilibrium climate sensitivity (ECS) to a doubling of atmospheric CO2, along with the transient climate response (TCR) and greenhouse gas emissions pathways, determines the amount of future warming. Coupled climate models have in the past been important tools to estimate and understand ECS. ECS estimated from Coupled Model Intercomparison Project Phase 5 (CMIP5) models lies between 2.0 and 4.7 K (mean of 3.2 K), whereas in the latest CMIP6 the spread has increased to 1.8–5.5 K (mean of 3.7 K), with 5 out of 25 models exceeding 5 K. It is thus pertinent to understand the causes underlying this shift. Here we compare the CMIP5 and CMIP6 model ensembles and find a systematic shift between CMIP eras to be unexplained as a process of random sampling from modeled forcing and feedback distributions. Instead, shortwave feedbacks shift towards more positive values, in particular over the Southern Ocean, driving the shift towards larger ECS values in many of the models. These results suggest that changes in model treatment of mixed-phase cloud processes and changes to Antarctic sea ice representation are likely causes of the shift towards larger ECS. Somewhat surprisingly, CMIP6 models exhibit less historical warming than CMIP5 models, despite an increase in TCR between CMIP eras (mean TCR increased from 1.7 to 1.9 K). The evolution of the warming suggests, however, that several of the CMIP6 models apply too strong aerosol cooling, resulting in too weak mid-20th century warming compared to the instrumental record.

Description: Source attribution and process analysis for atmospheric mercury in eastern China simulated by CMAQ-Hg Atmospheric Chemistry and Physics, 15, 8767-8779, 2015 Author(s): J. Zhu, T. Wang, J. Bieser, and V. Matthias The contribution from different emission sources and atmospheric processes to gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM), particulate bound mercury (PBM) and mercury deposition in eastern China were quantified using the Community Multi-scale Air Quality (CMAQ-Hg) modeling system run with a nested domain. Natural sources (NAT) and six categories of anthropogenic mercury sources (ANTH) including cement production (CEM), domestic life (DOM), industrial boilers (IND), metal production (MET), coal-fired power plants (PP) and traffic (TRA) were considered for source apportionment. NAT were responsible for 36.6 % of annual averaged GEM concentration, which was regarded as the most important source for GEM in spite of obvious seasonal variation. Among ANTH, the influence of MET and PP on GEM were most evident especially in winter. ANTH dominated the variations of GOM and PBM concentrations with contributions of 86.7 and 79.1 %, respectively. Among ANTH, IND were the largest contributor for GOM (57.5 %) and PBM (34.4 %) so that most mercury deposition came from IND. The effect of mercury emitted from out of China was indicated by a 〉 30 % contribution to GEM concentration and wet deposition. The contributions from nine processes – consisting of emissions (EMIS), gas-phase chemical production/loss (CHEM), horizontal advection (HADV), vertical advection (ZADV), horizontal advection (HDIF), vertical diffusion (VDIF), dry deposition (DDEP), cloud processes (CLDS) and aerosol processes (AERO) – were calculated for process analysis with their comparison in urban and non-urban regions of the Yangtze River delta (YRD). EMIS and VDIF affected surface GEM and PBM concentrations most and tended to compensate each other all the time in both urban and non-urban areas. However, DDEP was the most important removal process for GOM with 7.3 and 2.9 ng m −3 reduced in the surface of urban and non-urban areas, respectively, in 1 day. The diurnal profile variation of processes revealed the transportation of GOM from urban area to non-urban areas and the importance of CHEM/AERO in higher altitudes which partly caused diffusion of GOM downwards to non-urban areas. Most of the anthropogenic mercury was transported and diffused away from urban areas by HADV and VDIF and increased mercury concentrations in non-urban areas by HADV. Natural emissions only influenced CHEM and AERO more significantly than anthropogenic. Local emissions in the YRD contributed 8.5 % more to GEM and ~ 30 % more to GOM and PBM in urban areas compared to non-urban areas.

Description: Seasonal variation of secondary organic aerosol tracers in Central Tibetan Plateau Atmospheric Chemistry and Physics, 15, 8781-8793, 2015 Author(s): R.-Q. Shen, X. Ding, Q.-F. He, Z.-Y. Cong, Q.-Q. Yu, and X.-M. Wang Secondary organic aerosol (SOA) affects the earth's radiation balance and global climate. High-elevation areas are sensitive to global climate change. However, at present, SOA origins and seasonal variations are understudied in remote high-elevation areas. In this study, particulate samples were collected from July 2012 to July 2013 at the remote Nam Co (NC) site, Central Tibetan Plateau and analyzed for SOA tracers from biogenic (isoprene, monoterpenes and β-caryophyllene) and anthropogenic (aromatics) precursors. Among these compounds, isoprene SOA (SOA I ) tracers represented the majority (26.6 ± 44.2 ng m −3 ), followed by monoterpene SOA (SOA M ) tracers (0.97 ± 0.57 ng m −3 ), aromatic SOA (SOA A ) tracer (2,3-dihydroxy-4-oxopentanoic acid, DHOPA, 0.25 ± 0.18 ng m −3 ) and β-caryophyllene SOA tracer (β-caryophyllenic acid, 0.09 ± 0.10 ng m −3 ). SOA I tracers exhibited high concentrations in the summer and low levels in the winter. The similar temperature dependence of SOA I tracers and isoprene emission suggested that the seasonal variation of SOA I tracers at the NC site was mainly influenced by the isoprene emission. The ratio of high-NO x to low-NO x products of SOA I (2-methylglyceric acid to 2-methyltetrols) was highest in the winter and lowest in the summer, due to the influence of temperature and relative humidity. The seasonal variation of SOA M tracers was impacted by monoterpenes emission and gas-particle partitioning. During the summer to the fall, temperature effect on partitioning was the dominant process influencing SOA M tracers' variation; while the temperature effect on emission was the dominant process influencing SOA M tracers' variation during the winter to the spring. SOA M tracer levels did not elevate with increased temperature in the summer, probably resulting from the counteraction of temperature effects on emission and partitioning. The concentrations of DHOPA were 1–2 orders of magnitude lower than those reported in the urban regions of the world. Due to the transport of air pollutants from the adjacent Bangladesh and northeastern India, DHOPA presented relatively higher levels in the summer. In the winter when air masses mainly came from northwestern India, mass fractions of DHOPA in total tracers increased, although its concentrations declined. The SOA-tracer method was applied to estimate secondary organic carbon (SOC) from these four precursors. The annual average of SOC was 0.22 ± 0.29 μgC m −3 , with the biogenic SOC (sum of isoprene, monoterpenes and β-caryophyllene) accounting for 75 %. In the summer, isoprene was the major precursor with its SOC contributions of 81 %. In the winter when the emission of biogenic precursors largely dropped, the contributions of aromatic SOC increased. Our study implies that anthropogenic pollutants emitted in the Indian subcontinent could be transported to the TP and have an impact on SOC over the remote NC.

Description: Contrail life cycle and properties from 1 year of MSG/SEVIRI rapid-scan images Atmospheric Chemistry and Physics, 15, 8739-8749, 2015 Author(s): M. Vázquez-Navarro, H. Mannstein, and S. Kox The automatic contrail tracking algorithm (ACTA) – developed to automatically follow contrails as they age, drift and spread – enables the study of a large number of contrails and the evolution of contrail properties with time. In this paper we present a year's worth of tracked contrails, from August 2008 to July 2009 in order to derive statistically significant mean values. The tracking is performed using the 5 min rapid-scan mode of the Spinning Enhanced Visible and Infrared Imager (SEVIRI) on board the Meteosat Second Generation (MSG) satellites. The detection is based on the high spatial resolution of the images provided by the Moderate Resolution Imaging Spectroradiometer on board the Terra satellite (Terra/MODIS), where a contrail detection algorithm (CDA) is applied. The results show the satellite-derived average lifetimes of contrails and contrail-cirrus along with the probability density function (PDF) of other geometric characteristics such as mean coverage, distribution and width. In combination with specifically developed algorithms (RRUMS; Rapid Retrieval of Upwelling irradiance from MSG/SEVIRI and COCS (Cirrus Optical properties derived from CALIOP and SEVIRI), explained below) it is possible to derive the radiative forcing (RF), energy forcing (EF), optical thickness (τ) and altitude of the tracked contrails. Mean values here retrieved are duration, 1 h; length, 130 km; width, 8 km; altitude, 11.7 km; optical thickness, 0.34. Radiative forcing and energy forcing are shown for land/water backgrounds in day/night situations.

Description: A comparison of chemical mechanisms using tagged ozone production potential (TOPP) analysis Atmospheric Chemistry and Physics, 15, 8795-8808, 2015 Author(s): J. Coates and T. M. Butler Ground-level ozone is a secondary pollutant produced photochemically from reactions of NO x with peroxy radicals produced during volatile organic compound (VOC) degradation. Chemical transport models use simplified representations of this complex gas-phase chemistry to predict O 3 levels and inform emission control strategies. Accurate representation of O 3 production chemistry is vital for effective prediction. In this study, VOC degradation chemistry in simplified mechanisms is compared to that in the near-explicit Master Chemical Mechanism (MCM) using a box model and by "tagging" all organic degradation products over multi-day runs, thus calculating the tagged ozone production potential (TOPP) for a selection of VOCs representative of urban air masses. Simplified mechanisms that aggregate VOC degradation products instead of aggregating emitted VOCs produce comparable amounts of O 3 from VOC degradation to the MCM. First-day TOPP values are similar across mechanisms for most VOCs, with larger discrepancies arising over the course of the model run. Aromatic and unsaturated aliphatic VOCs have the largest inter-mechanism differences on the first day, while alkanes show largest differences on the second day. Simplified mechanisms break VOCs down into smaller-sized degradation products on the first day faster than the MCM, impacting the total amount of O 3 produced on subsequent days due to secondary chemistry.

Description: Trace metal characterization of aerosol particles and cloud water during HCCT 2010 Atmospheric Chemistry and Physics, 15, 8751-8765, 2015 Author(s): K. W. Fomba, D. van Pinxteren, K. Müller, Y. Iinuma, T. Lee, J. L. Collett Jr., and H. Herrmann Trace metal characterization of bulk and size-resolved aerosol and cloud water samples were performed during the Hill Cap Cloud Thuringia (HCCT) campaign. Cloud water was collected at the top of Mt. Schmücke while aerosol samples were collected at two stations upwind and downwind of Mt. Schmücke. Fourteen trace metals including Ti, V, Fe, Mn, Co, Zn, Ni, Cu, As, Sr, Rb, Pb, Cr, and Se were investigated during four full cloud events (FCEs) that fulfilled the conditions of a continuous air mass flow through the three stations. Aerosol particle trace metal concentrations were found to be lower than those observed in the same region during previous field experiments but were within a similar range to those observed in other rural regions in Europe. Fe and Zn were the most abundant elements with concentration ranges of 0.2–111.6 and 1.1–32.1 ng m −3 , respectively. Fe, Mn, and Ti were mainly found in coarse mode aerosols while Zn, Pb, and As were mostly found in the fine mode. Correlation and enrichment factor analysis of trace metals revealed that trace metals such as Ti and Rb were mostly of crustal origin while trace metals such as Zn, Pb, As, Cr, Ni, V, and Cu were of anthropogenic origin. Trace metals such as Fe and Mn were of mixed origins including crustal and combustion sources. Trace metal cloud water concentration decreased from Ti, Mn, Cr, to Co with average concentrations of 9.18, 5.59, 5.54, and 0.46 μg L −1 , respectively. A non-uniform distribution of soluble Fe, Cu, and Mn was observed across the cloud drop sizes. Soluble Fe and Cu were found mainly in cloud droplets with diameters between 16 and 22 μm, while Mn was found mostly in larger drops greater than 22 μm. Fe(III) was the main form of soluble Fe especially in the small and larger drops with concentrations ranging from 2.2 to 37.1 μg L −1 . In contrast to other studies, Fe(II) was observed mainly in the evening hours, implying its presence was not directly related to photochemical processes. Aerosol–cloud interaction did not lead to a marked increase in soluble trace metal concentrations; rather it led to differences in the chemical composition of the aerosol due to preferential loss of aerosol particles through physical processes including cloud drop deposition to vegetative surfaces.

Description: New fire diurnal cycle characterizations to improve fire radiative energy assessments made from MODIS observations Atmospheric Chemistry and Physics, 15, 8831-8846, 2015 Author(s): N. Andela, J. W. Kaiser, G. R. van der Werf, and M. J. Wooster Accurate near real time fire emissions estimates are required for air quality forecasts. To date, most approaches are based on satellite-derived estimates of fire radiative power (FRP), which can be converted to fire radiative energy (FRE) which is directly related to fire emissions. Uncertainties in these FRE estimates are often substantial. This is for a large part because the most often used low-Earth orbit satellite-based instruments such as the Moderate Resolution Imaging Spectroradiometer (MODIS) have a relatively poor sampling of the usually pronounced fire diurnal cycle. In this paper we explore the spatial variation of this fire diurnal cycle and its drivers using data from the geostationary Meteosat Spinning Enhanced Visible and Infrared Imager (SEVIRI). In addition, we sampled data from the SEVIRI instrument at MODIS detection opportunities to develop two approaches to estimate hourly FRE based on MODIS active fire detections. The first approach ignored the fire diurnal cycle, assuming persistent fire activity between two MODIS observations, while the second approach combined knowledge on the climatology of the fire diurnal cycle with active fire detections to estimate hourly FRE. The full SEVIRI time series, providing full coverage of the fire diurnal cycle, were used to evaluate the results. Our study period comprised of 3 years (2010–2012), and we focused on Africa and the Mediterranean basin to avoid the use of potentially lower quality SEVIRI data obtained at very far off-nadir view angles. We found that the fire diurnal cycle varies substantially over the study region, and depends on both fuel and weather conditions. For example, more "intense" fires characterized by a fire diurnal cycle with high peak fire activity, long duration over the day, and with nighttime fire activity are most common in areas of large fire size (i.e., large burned area per fire event). These areas are most prevalent in relatively arid regions. Ignoring the fire diurnal cycle generally resulted in an overestimation of FRE, while including information on the climatology of the fire diurnal cycle improved FRE estimates. The approach based on knowledge of the climatology of the fire diurnal cycle also improved distribution of FRE over the day, although only when aggregating model results to coarser spatial and/or temporal scale good correlation was found with the full SEVIRI hourly reference data set. We recommend the use of regionally varying fire diurnal cycle information within the Global Fire Assimilation System (GFAS) used in the Copernicus Atmosphere Monitoring Services, which will improve FRE estimates and may allow for further reconciliation of biomass burning emission estimates from different inventories.

Description: The anthropogenic contribution to atmospheric black carbon concentrations in southern Africa: a WRF-Chem modeling study Atmospheric Chemistry and Physics, 15, 8809-8830, 2015 Author(s): F. Kuik, A. Lauer, J. P. Beukes, P. G. Van Zyl, M. Josipovic, V. Vakkari, L. Laakso, and G. T. Feig South Africa has one of the largest industrialized economies in Africa. Emissions of air pollutants are particularly high in the Johannesburg-Pretoria metropolitan area, the Mpumalanga Highveld and the Vaal Triangle, resulting in local air pollution. This study presents and evaluates a setup for conducting modeling experiments over southern Africa with the Weather Research and Forecasting model including chemistry and aerosols (WRF-Chem), and analyzes the contribution of anthropogenic emissions to the total black carbon (BC) concentrations from September to December 2010. The modeled BC concentrations are compared with measurements obtained at the Welgegund station situated ca. 100 km southwest of Johannesburg. An evaluation of WRF-Chem with observational data from ground-based measurement stations, radiosondes, and satellites shows that the meteorology is modeled mostly reasonably well, but precipitation amounts are widely overestimated and the onset of the wet season is modeled approximately 1 month too early in 2010. Modeled daily mean BC concentrations show a temporal correlation of 0.66 with measurements, but the total BC concentration is underestimated in the model by up to 50 %. Sensitivity studies with anthropogenic emissions of BC and co-emitted species turned off show that anthropogenic sources can contribute up to 100 % to BC concentrations in the industrialized and urban areas, and anthropogenic BC and co-emitted species together can contribute up to 60 % to PM 1 levels. Particularly the co-emitted species contribute significantly to the aerosol optical depth (AOD). Furthermore, in areas of large-scale biomass-burning atmospheric heating rates are increased through absorption by BC up to an altitude of about 600hPa.

Description: Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site Atmospheric Chemistry and Physics, 15, 8871-8888, 2015 Author(s): S. H. Budisulistiorini, X. Li, S. T. Bairai, J. Renfro, Y. Liu, Y. J. Liu, K. A. McKinney, S. T. Martin, V. F. McNeill, H. O. T. Pye, A. Nenes, M. E. Neff, E. A. Stone, S. Mueller, C. Knote, S. L. Shaw, Z. Zhang, A. Gold, and J. D. Surratt A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM 2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated ( r 2 〉 0.7) with 2-methyltetrols, C 5 -alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m −3 ). Particle-phase sulfate is fairly correlated ( r 2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated ( r 2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NO y ; r 2 = 0.38) and nitrate ( r 2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy ( r 2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Description: Secondary organic aerosol formation from photochemical aging of light-duty gasoline vehicle exhausts in a smog chamber Atmospheric Chemistry and Physics, 15, 9049-9062, 2015 Author(s): T. Liu, X. Wang, W. Deng, Q. Hu, X. Ding, Y. Zhang, Q. He, Z. Zhang, S. Lü, X. Bi, J. Chen, and J. Yu In China, a rapid increase in passenger vehicles has led to the growing concern of vehicle exhaust as an important source of anthropogenic secondary organic aerosol (SOA) in megacities hard hit by haze. In this study, the SOA formation of emissions from two idling light-duty gasoline vehicles (LDGVs) (Euro 1 and Euro 4) operated in China was investigated in a 30 m 3 smog chamber. Five photo-oxidation experiments were carried out at 25 °C with relative humidity at around 50 %. After aging at an OH exposure of 5 × 10 6 molecules cm −3 h, the formed SOA was 12–259 times as high as primary organic aerosol (POA). The SOA production factors (PF) were 0.001–0.044 g kg −1 fuel, comparable with those from the previous studies at comparable OH exposure. This quite lower OH exposure than that in typical atmospheric conditions might however lead to the underestimation of the SOA formation potential from LDGVs. Effective SOA yields in this study were well fit by a one-product gas-particle partitioning model but quite lower than those of a previous study investigating SOA formation from three idling passenger vehicles (Euro 2–4). Traditional single-ring aromatic precursors and naphthalene could explain 51–90 % of the formed SOA. Unspeciated species such as branched and cyclic alkanes might be the possible precursors for the unexplained SOA. A high-resolution time-of-flight aerosol mass spectrometer was used to characterize the chemical composition of SOA. The relationship between f 43 (ratio of m/z 43, mostly C 2 H 3 O + , to the total signal in mass spectrum) and f 44 (mostly CO 2 + ) of the gasoline vehicle exhaust SOA is similar to the ambient semi-volatile oxygenated organic aerosol (SV-OOA). We plot the O : C and H : C molar ratios of SOA in a Van Krevelen diagram. The slopes of ΔH : C / ΔO : C ranged from −0.59 to −0.36, suggesting that the oxidation chemistry in these experiments was a combination of carboxylic acid and alcohol/peroxide formation.

Description: Uncertainties in global aerosols and climate effects due to biofuel emissions Atmospheric Chemistry and Physics, 15, 8577-8596, 2015 Author(s): J. K. Kodros, C. E. Scott, S. C. Farina, Y. H. Lee, C. L'Orange, J. Volckens, and J. R. Pierce Aerosol emissions from biofuel combustion impact both health and climate; however, while reducing emissions through improvements to combustion technologies will improve health, the net effect on climate is largely unconstrained. In this study, we examine sensitivities in global aerosol concentration, direct radiative climate effect, and cloud-albedo aerosol indirect climate effect to uncertainties in biofuel emission factors, optical mixing state, and model nucleation and background secondary organic aerosol (SOA). We use the Goddard Earth Observing System global chemical-transport model (GEOS-Chem) with TwO Moment Aerosol Sectional (TOMAS) microphysics. The emission factors include amount, composition, size, and hygroscopicity, as well as optical mixing-state properties. We also evaluate emissions from domestic coal use, which is not biofuel but is also frequently emitted from homes. We estimate the direct radiative effect assuming different mixing states (homogeneous, core-shell, and external) with and without absorptive organic aerosol (brown carbon). We find the global-mean direct radiative effect of biofuel emissions ranges from −0.02 to +0.06 W m −2 across all simulation/mixing-state combinations with regional effects in source regions ranging from −0.2 to +0.8 W m −2 . The global-mean cloud-albedo aerosol indirect effect (AIE) ranges from +0.01 to −0.02 W m −2 with regional effects in source regions ranging from −1.0 to −0.05 W m −2 . The direct radiative effect is strongly dependent on uncertainties in emissions mass, composition, emissions aerosol size distributions, and assumed optical mixing state, while the indirect effect is dependent on the emissions mass, emissions aerosol size distribution, and the choice of model nucleation and secondary organic aerosol schemes. The sign and magnitude of these effects have a strong regional dependence. We conclude that the climate effects of biofuel aerosols are largely unconstrained, and the overall sign of the aerosol effects is unclear due to uncertainties in model inputs. This uncertainty limits our ability to introduce mitigation strategies aimed at reducing biofuel black carbon emissions in order to counter warming effects from greenhouse gases. To better understand the climate impact of particle emissions from biofuel combustion, we recommend field/laboratory measurements to narrow constraints on (1) emissions mass, (2) emission size distribution, (3) mixing state, and (4) ratio of black carbon to organic aerosol.

Description: A two-layer canopy model with thermal inertia for an improved snowpack energy balance below needleleaf forest (model SNOWPACK, version 3.2.1, revision 741) Geoscientific Model Development, 8, 2379-2398, 2015 Author(s): I. Gouttevin, M. Lehning, T. Jonas, D. Gustafsson, and M. Mölder A new, two-layer canopy module with thermal inertia as part of the detailed snow model SNOWPACK (version 3.2.1) is presented and evaluated. As a by-product of these new developments, an exhaustive description of the canopy module of the SNOWPACK model is provided, thereby filling a gap in the existing literature. In its current form, the two-layer canopy module is suited for evergreen needleleaf forest, with or without snow cover. It is designed to reproduce the difference in thermal response between leafy and woody canopy elements, and their impact on the underlying snowpack or ground surface energy balance. Given the number of processes resolved, the SNOWPACK model with its enhanced canopy module constitutes a sophisticated physics-based modeling chain of the continuum going from atmosphere to soil through the canopy and snow. Comparisons of modeled sub-canopy thermal radiation to stand-scale observations at an Alpine site (Alptal, Switzerland) demonstrate improvements induced by the new canopy module. Both thermal heat mass and the two-layer canopy formulation contribute to reduce the daily amplitude of the modeled canopy temperature signal, in agreement with observations. Particularly striking is the attenuation of the nighttime drop in canopy temperature, which was a key model bias. We specifically show that a single-layered canopy model is unable to produce this limited temperature drop correctly. The impact of the new parameterizations on the modeled dynamics of the sub-canopy snowpack is analyzed. The new canopy module yields consistent results but the frequent occurrence of mixed-precipitation events at Alptal prevents a conclusive assessment of model performance against snow data. The new model is also successfully tested without specific tuning against measured tree temperature and biomass heat-storage fluxes at the boreal site of Norunda (Sweden). This provides an independent assessment of its physical consistency and stresses the robustness and transferability of the chosen parameterizations. The SNOWPACK code including the new canopy module, is available under Gnu General Public License (GPL) license and upon creation of an account at https://models.slf.ch/ .

Description: Patterns in atmospheric carbonaceous aerosols in China: emission estimates and observed concentrations Atmospheric Chemistry and Physics, 15, 8657-8678, 2015 Author(s): H. Cui, P. Mao, Y. Zhao, C. P. Nielsen, and J. Zhang China is experiencing severe carbonaceous aerosol pollution driven mainly by large emissions resulting from intensive use of solid fuels. To gain a better understanding of the levels and trends of carbonaceous aerosol emissions and the resulting ambient concentrations at the national scale, we update an emission inventory of anthropogenic organic carbon (OC) and elemental carbon (EC) and employ existing observational studies to analyze characteristics of these aerosols including temporal, spatial, and size distributions, and the levels and shares of secondary organic carbon (SOC) in total OC. We further use ground observations to test the levels and inter-annual trends of the calculated national and provincial emissions of carbonaceous aerosols, and propose possible improvements in emission estimation for the future. The national OC emissions are estimated to have increased 29 % from 2000 (2127 Gg) to 2012 (2749 Gg) and EC by 37 % (from 1356 to 1857 Gg). The residential, industrial, and transportation sectors contributed an estimated 74–78, 17–21, and 4–6 % of the total emissions of OC, respectively, and 49–55, 30–34, and 14–18 % of EC. Updated emission factors (EFs) based on the most recent local field measurements, particularly for biofuel stoves, led to considerably lower emissions of OC compared to previous inventories. Compiling observational data across the country, higher concentrations of OC and EC are found in northern and inland cities, while higher OC / EC ratios are found in southern sites, due to the joint effects of primary emissions and meteorology. Higher OC / EC ratios are estimated at rural and remote sites compared to urban ones, attributed to more emissions of OC from biofuel use, more biogenic emissions of volatile organic compound (VOC) precursors to SOC, and/or transport of aged aerosols. For most sites, higher concentrations of OC, EC, and SOC are observed in colder seasons, while SOC / OC is reduced, particularly at rural and remote sites, attributed partly to weaker atmospheric oxidation and SOC formation compared to summer. Enhanced SOC formation from oxidization and anthropogenic activities like biomass combustion is judged to have crucial effects on severe haze events characterized by high particle concentrations. Several observational studies indicate an increasing trend in ambient OC / EC (but not in OC or EC individually) from 2000 to 2010, confirming increased atmospheric oxidation of OC across the country. Combining the results of emission estimation and observations, the improvement over prior emission inventories is indicated by inter-annual comparisons and correlation analysis. It is also indicated, however, that the estimated growth in emissions might be faster than observed growth, and that some sources with high primary OC / EC, such as burning of biomass, are still underestimated. Further studies to determine changing EFs over time in the residential sector and to compare to other measurements, such as satellite observations, are thus suggested to improve understanding of the levels and trends of primary carbonaceous aerosol emissions in China.

Description: A new model of the global biogeochemical cycle of carbonyl sulfide – Part 2: Use of carbonyl sulfide to constrain gross primary productivity in current vegetation models Atmospheric Chemistry and Physics, 15, 9285-9312, 2015 Author(s): T. Launois, P. Peylin, S. Belviso, and B. Poulter Clear analogies between carbonyl sulfide (OCS) and carbon dioxide (CO 2 ) diffusion pathways through leaves have been revealed by experimental studies, with plant uptake playing an important role for the atmospheric budget of both species. Here we use atmospheric OCS to evaluate the gross primary production (GPP) of three dynamic global vegetation models (Lund–Potsdam–Jena, LPJ; National Center for Atmospheric Research – Community Land Model 4, NCAR-CLM4; and Organising Carbon and Hydrology In Dynamic Ecosystems, ORCHIDEE). Vegetation uptake of OCS is modeled as a linear function of GPP and leaf relative uptake (LRU), the ratio of OCS to CO 2 deposition velocities of plants. New parameterizations for the non-photosynthetic sinks (oxic soils, atmospheric oxidation) and biogenic sources (oceans and anoxic soils) of OCS are also provided. Despite new large oceanic emissions, global OCS budgets created with each vegetation model show exceeding sinks by several hundred Gg S yr −1 . An inversion of the surface fluxes (optimization of a global scalar which accounts for flux uncertainties) led to balanced OCS global budgets, as atmospheric measurements suggest, mainly by drastic reduction (up to −50 %) in soil and vegetation uptakes. The amplitude of variations in atmospheric OCS mixing ratios is mainly dictated by the vegetation sink over the Northern Hemisphere. This allows for bias recognition in the GPP representations of the three selected models. The main bias patterns are (i) the terrestrial GPP of ORCHIDEE at high northern latitudes is currently overestimated, (ii) the seasonal variations of the GPP are out of phase in the NCAR-CLM4 model, showing a maximum carbon uptake too early in spring in the northernmost ecosystems, (iii) the overall amplitude of the seasonal variations of GPP in NCAR-CLM4 is too small, and (iv) for the LPJ model, the GPP is slightly out of phase for the northernmost ecosystems and the respiration fluxes might be too large in summer in the Northern Hemisphere. These results rely on the robustness of the OCS modeling framework and, in particular, the choice of the LRU values (assumed constant in time) and the parameterization of soil OCS uptake with small seasonal variations. Refined optimization with regional-scale and seasonally varying coefficients might help to test some of these hypothesis.

Description: Impacts of an unknown daytime HONO source on the mixing ratio and budget of HONO, and hydroxyl, hydroperoxyl, and organic peroxy radicals, in the coastal regions of China Atmospheric Chemistry and Physics, 15, 9381-9398, 2015 Author(s): Y. Tang, J. An, F. Wang, Y. Li, Y. Qu, Y. Chen, and J. Lin Many field experiments have found high nitrous acid (HONO) mixing ratios in both urban and rural areas during daytime, but these high daytime HONO mixing ratios cannot be explained well by gas-phase production, HONO emissions, and nighttime hydrolysis conversion of nitrogen dioxide (NO 2 ) on aerosols, suggesting that an unknown daytime HONO source ( P unknown ) could exist. The formula P unknown ≈ 19.60[NO 2 ] · J (NO 2 ) was obtained using observed data from 13 field experiments across the globe. The three additional HONO sources (i.e., the P unknown , nighttime hydrolysis conversion of NO 2 on aerosols, and HONO emissions) were coupled into the WRF-Chem model (Weather Research and Forecasting model coupled with Chemistry) to assess the P unknown impacts on the concentrations and budgets of HONO and peroxy (hydroxyl, hydroperoxyl, and organic peroxy) radicals (RO x ) (= OH + HO 2 + RO 2 ) in the coastal regions of China. Results indicated that the additional HONO sources produced a significant improvement in HONO and OH simulations, particularly in the daytime. High daytime average P unknown values were found in the coastal regions of China, with a maximum of 2.5 ppb h −1 in the Beijing–Tianjin–Hebei region. The P unknown produced a 60–250 % increase of OH, HO 2 , and RO 2 near the ground in the major cities of the coastal regions of China, and a 5–48 % increase of OH, HO 2 , and RO 2 in the daytime meridional-mean mixing ratios within 1000 m above the ground. When the three additional HONO sources were included, the photolysis of HONO was the second most important source in the OH production rate in Beijing, Shanghai, and Guangzhou before 10:00 LST with a maximum of 3.72 ppb h −1 and a corresponding P unknown contribution of 3.06 ppb h −1 in Beijing, whereas the reaction of HO 2 + NO (nitric oxide) was dominant after 10:00 LST with a maximum of 9.38 ppb h −1 and a corresponding P unknown contribution of 7.23 ppb h −1 in Beijing. The whole RO x cycle was accelerated by the three additional HONO sources, especially the P unknown . The daytime average OH production rate was enhanced by 0.67 due to the three additional HONO sources; [0.64], due to the P unknown , to 4.32 [3.86] ppb h −1 , via the reaction of HO 2 + NO, and by 0.49 [0.47] to 1.86 [1.86] ppb h −1 , via the photolysis of HONO. The OH daytime average loss rate was enhanced by 0.58 [0.55] to 2.03 [1.92] ppb h −1 , via the reaction of OH + NO 2 , and by 0.31 [0.28] to 1.78 [1.64] ppb h −1 , via the reaction of OH + CO (carbon monoxide) in Beijing, Shanghai, and Guangzhou. Similarly, the three additional HONO sources produced an increase of 0.31 [0.28] (with a corresponding P unknown contribution) to 1.78 [1.64] ppb h −1 , via the reaction of OH + CO, and 0.10 [0.09] to 0.63 [0.59] ppb h −1 , via the reaction of CH 3 O 2 (methylperoxy radical) + NO in the daytime average HO 2 production rate, and 0.67 [0.61] to 4.32 [4.27] ppb h −1 , via the reaction of HO 2 + NO in the daytime average HO 2 loss rate in Beijing, Shanghai, and Guangzhou. The above results suggest that the P unknown considerably enhanced the RO x concentrations and accelerated RO x cycles in the coastal regions of China, and could produce significant increases in concentrations of inorganic aerosols and secondary organic aerosols and further aggravate haze events in these regions.

Description: Particulate organic nitrates observed in an oil and natural gas production region during wintertime Atmospheric Chemistry and Physics, 15, 9313-9325, 2015 Author(s): L. Lee, P. J. Wooldridge, J. deGouw, S. S. Brown, T. S. Bates, P. K. Quinn, and R. C. Cohen Organic nitrates in both gas and condensed (aerosol) phases were measured during the Uintah Basin Winter Ozone Study from January to February in 2012. A high degree of correlation between total aerosol volume at diameters less than 500 nm and the particulate organic nitrate concentration indicates that organic nitrates are a consistent, if not dominant, fraction of fine aerosol mass. In contrast, a similar correlation with sub-2.5 μm aerosol volume is weaker. The C : N atomic ratio inferred from field measurements of PM 2.5 and particulate organic nitrate is 34 : 1. Calculations constrained by the observations indicate that both condensation of gas-phase nitrates and heterogeneous reactions of NO 3 / N 2 O 5 are responsible for introducing organic nitrate functionality into the aerosol and that the source molecules are alkanes. Extrapolating the results to urban aerosol suggests organic nitrate production from alkanes may be a major secondary organic aerosol source.

Description: The influences of mass loading and rapid dilution of secondary organic aerosol on particle volatility Atmospheric Chemistry and Physics, 15, 9327-9343, 2015 Author(s): K. R. Kolesar, C. Chen, D. Johnson, and C. D. Cappa The thermally induced evaporation of secondary organic aerosol (SOA) has been characterized for SOA formed from the dark ozonolysis of α-pinene at initial mass concentrations ranging from 1 to 800 μg m −3 . Temperature-dependent particle size distributions were measured using a thermodenuder and the resulting mass thermograms were compared between the SOA formed at the various SOA mass concentrations. Negligible differences were observed between the mass thermograms for SOA concentrations 〈 300 μg m −3 . At higher SOA concentrations, the observed mass thermograms indicated the SOA was actually slightly less volatile than the SOA at lower concentrations; this is likely an artifact due to either saturation of the gas phase or to recondensation during cooling. The thermograms observed when the SOA was formed at high concentrations (〉 380 μg m −3 ) and then rapidly isothermally diluted to low concentrations (1–20 μg m −3 ) were identical to those for the SOA that was initially formed at low concentrations. The experimental results were compared to a kinetic model that simulates particle evaporation upon heating in a thermodenuder for a given input volatility distribution and particle composition. Three cases were considered: (1) the SOA was composed of semi-volatile monomer species with a volatility distribution based on that derived previously from consideration of SOA growth experiments; (2) the initial SOA was composed almost entirely of non-volatile dimers that decompose upon heating into their semi-volatile monomer units, which can then evaporate; and (3) where a volatility distribution was derived by fitting the model to the observed mass thermograms. It was found that good agreement is obtained between model predictions and the observations when the particle composition is dominated by either compounds of low volatility or by dimers. These same models were used to simulate isothermal evaporation of the SOA and were found to be broadly consistent with literature observations that indicate that SOA evaporation occurs with multiple timescales. The use of the semi-volatile monomer volatility distribution fails to reproduce the observed evaporation. The presence of dimers and larger oligomers in secondary organic aerosol formed from products of the reaction of α-pinene and O 3 has been well established in laboratory studies. However, the timescale and relative importance of the formation of oligomers or low-volatility compounds in the growth and evaporation of SOA has been debated. This study provides further support that low-volatility compounds and oligomers are formed in α-pinene + O 3 in high abundances and suggests that their formation occurs rapidly upon particle formation.

Description: Current model capabilities for simulating black carbon and sulfate concentrations in the Arctic atmosphere: a multi-model evaluation using a comprehensive measurement data set Atmospheric Chemistry and Physics, 15, 9413-9433, 2015 Author(s): S. Eckhardt, B. Quennehen, D. J. L. Olivié, T. K. Berntsen, R. Cherian, J. H. Christensen, W. Collins, S. Crepinsek, N. Daskalakis, M. Flanner, A. Herber, C. Heyes, Ø. Hodnebrog, L. Huang, M. Kanakidou, Z. Klimont, J. Langner, K. S. Law, M. T. Lund, R. Mahmood, A. Massling, S. Myriokefalitakis, I. E. Nielsen, J. K. Nøjgaard, J. Quaas, P. K. Quinn, J.-C. Raut, S. T. Rumbold, M. Schulz, S. Sharma, R. B. Skeie, H. Skov, T. Uttal, K. von Salzen, and A. Stohl The concentrations of sulfate, black carbon (BC) and other aerosols in the Arctic are characterized by high values in late winter and spring (so-called Arctic Haze) and low values in summer. Models have long been struggling to capture this seasonality and especially the high concentrations associated with Arctic Haze. In this study, we evaluate sulfate and BC concentrations from eleven different models driven with the same emission inventory against a comprehensive pan-Arctic measurement data set over a time period of 2 years (2008–2009). The set of models consisted of one Lagrangian particle dispersion model, four chemistry transport models (CTMs), one atmospheric chemistry-weather forecast model and five chemistry climate models (CCMs), of which two were nudged to meteorological analyses and three were running freely. The measurement data set consisted of surface measurements of equivalent BC (eBC) from five stations (Alert, Barrow, Pallas, Tiksi and Zeppelin), elemental carbon (EC) from Station Nord and Alert and aircraft measurements of refractory BC (rBC) from six different campaigns. We find that the models generally captured the measured eBC or rBC and sulfate concentrations quite well, compared to previous comparisons. However, the aerosol seasonality at the surface is still too weak in most models. Concentrations of eBC and sulfate averaged over three surface sites are underestimated in winter/spring in all but one model (model means for January–March underestimated by 59 and 37 % for BC and sulfate, respectively), whereas concentrations in summer are overestimated in the model mean (by 88 and 44 % for July–September), but with overestimates as well as underestimates present in individual models. The most pronounced eBC underestimates, not included in the above multi-site average, are found for the station Tiksi in Siberia where the measured annual mean eBC concentration is 3 times higher than the average annual mean for all other stations. This suggests an underestimate of BC sources in Russia in the emission inventory used. Based on the campaign data, biomass burning was identified as another cause of the modeling problems. For sulfate, very large differences were found in the model ensemble, with an apparent anti-correlation between modeled surface concentrations and total atmospheric columns. There is a strong correlation between observed sulfate and eBC concentrations with consistent sulfate/eBC slopes found for all Arctic stations, indicating that the sources contributing to sulfate and BC are similar throughout the Arctic and that the aerosols are internally mixed and undergo similar removal. However, only three models reproduced this finding, whereas sulfate and BC are weakly correlated in the other models. Overall, no class of models (e.g., CTMs, CCMs) performed better than the others and differences are independent of model resolution.

Description: Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs Atmospheric Chemistry and Physics, 15, 9435-9453, 2015 Author(s): G. Shi, A. M. Buffen, M. G. Hastings, C. Li, H. Ma, Y. Li, B. Sun, C. An, and S. Jiang Snowpits along a traverse from coastal East Antarctica to the summit of the ice sheet (Dome Argus) are used to investigate the post-depositional processing of nitrate (NO 3 − ) in snow. Seven snowpits from sites with accumulation rates between 24 and 172 kg m −2 a −1 were sampled to depths of 150 to 300 cm. At sites from the continental interior (low accumulation, 〈 55 kg m −2 a −1 ), nitrate mass fraction is generally 〉 200 ng g −1 in surface snow and decreases quickly with depth to 〈 50 ng g −1 . Considerably increasing values of δ 15 N of nitrate are also observed (16–461 ‰ vs. air N 2 ), particularly in the top 20 cm, which is consistent with predicted fractionation constants for the photolysis of nitrate. The δ 18 O of nitrate (17–84 ‰ vs. VSMOW (Vienna Standard Mean Ocean Water)), on the other hand, decreases with increasing δ 15 N, suggestive of secondary formation of nitrate in situ (following photolysis) with a low δ 18 O source. Previous studies have suggested that δ 15 N and δ 18 O of nitrate at deeper snow depths should be predictable based upon an exponential change derived near the surface. At deeper depths sampled in this study, however, the relationship between nitrate mass fraction and δ 18 O changes, with increasing δ 18 O of nitrate observed between 100 and 200 cm. Predicting the impact of post-depositional loss, and therefore changes in the isotopes with depth, is highly sensitive to the depth interval over which an exponential change is assumed. In the snowpits collected closer to the coast (accumulation 〉 91 kg m −2 a −1 ), there are no obvious trends detected with depth and instead seasonality in nitrate mass fraction and isotopic composition is found. In comparison to the interior sites, the coastal pits are lower in δ 15 N (−15–71 ‰ vs. air N 2 ) and higher in δ 18 O of nitrate (53–111 ‰ vs. VSMOW). The relationships found amongst mass fraction, δ 15 N, δ 18 O and Δ 17 O (Δ 17 O = δ 17 O–0.52 × δ 18 O) of nitrate cannot be explained by local post-depositional processes alone, and are instead interpreted in the context of a primary atmospheric signal. Consistent with other Antarctic observational and modeling studies, the isotopic results are suggestive of an important influence of stratospheric ozone chemistry on nitrate formation during the cold season and a mix of tropospheric sources and chemistry during the warm season. Overall, the findings in this study speak to the sensitivity of nitrate isotopic composition to post-depositional processing and highlight the strength of combined use of the nitrogen and oxygen isotopes for a mechanistic understanding of this processing.

Description: NO x emission estimates during the 2014 Youth Olympic Games in Nanjing Atmospheric Chemistry and Physics, 15, 9399-9412, 2015 Author(s): J. Ding, R. J. van der A, B. Mijling, P. F. Levelt, and N. Hao The Nanjing Government applied temporary environmental regulations to guarantee good air quality during the Youth Olympic Games (YOG) in 2014. We study the effect of those regulations by applying the emission estimate algorithm DECSO (Daily Emission estimates Constrained by Satellite Observations) to measurements of the Ozone Monitoring Instrument (OMI). We improved DECSO by updating the chemical transport model CHIMERE from v2006 to v2013 and by adding an Observation minus Forecast (OmF) criterion to filter outlying satellite retrievals due to high aerosol concentrations. The comparison of model results with both ground and satellite observations indicates that CHIMERE v2013 is better performing than CHIMERE v2006. After filtering the satellite observations with high aerosol loads that were leading to large OmF values, unrealistic jumps in the emission estimates are removed. Despite the cloudy conditions during the YOG we could still see a decrease of tropospheric NO 2 column concentrations of about 32 % in the OMI observations when compared to the average NO 2 columns from 2005 to 2012. The results of the improved DECSO algorithm for NO x emissions show a reduction of at least 25 % during the YOG period and afterwards. This indicates that air quality regulations taken by the local government have an effect in reducing NO x emissions. The algorithm is also able to detect an emission reduction of 10 % during the Chinese Spring Festival. This study demonstrates the capacity of the DECSO algorithm to capture the change of NO x emissions on a monthly scale. We also show that the observed NO 2 columns and the derived emissions show different patterns that provide complimentary information. For example, the Nanjing smog episode in December 2013 led to a strong increase in NO 2 concentrations without an increase in NO x emissions. Furthermore, DECSO gives us important information on the non-trivial seasonal relation between NO x emissions and NO 2 concentrations on a local scale.

Description: Observations of atmospheric mercury in China: a critical review Atmospheric Chemistry and Physics, 15, 9455-9476, 2015 Author(s): X. W. Fu, H. Zhang, B. Yu, X. Wang, C.-J. Lin, and X. B. Feng China presently contributes the largest amount of anthropogenic mercury (Hg) emission into the atmosphere in the world. Over the past decade, numerous studies have been conducted to characterize the concentration and forms of atmospheric Hg in China, which provide insights into the spatial and temporal distributions of atmospheric Hg through ground-based measurements at widely diverse geographical locations and during cruise and flight campaigns. In this paper, we present a comprehensive review of the state of understanding in atmospheric Hg in China. Gaseous elemental mercury (GEM) and particulate-bound mercury (PBM) measured at the remote sites in China are substantially elevated compared to the background values in the Northern Hemisphere. In Chinese urban areas, the highly elevated GEM, PBM and gaseous oxidized mercury (GOM) were mainly derived from local anthropogenic Hg emissions, whereas regional anthropogenic emissions and long-range transport from domestic source regions are the primary causes of the elevated GEM and PBM concentrations at remote sites. Using 7–9 years of continuous observations at a remote site and an urban site, a slight increase in atmospheric GEM (2.4–2.5 % yr −1 ) was identified (paired samples test: p 〈 0.01), which is in agreement with the increasing domestic anthropogenic emissions. Anthropogenic GEM emission quantity in China estimated through the observed GEM / CO concentration ratios ranged from 632 to 1138 t annually over the past decade, 2–3 times larger than published values using emission activity data. Modeling results and filed measurements show dry deposition is the predominant process for removing Hg from the atmosphere, 2.5–9.0 times larger than wet deposition, due to the elevated atmospheric GEM and PBM concentrations that facilitate dry deposition to terrestrial landscapes. Further studies to reconcile the observed and simulated Hg concentrations, to understand the impact of domestic emission reduction on Hg concentration and deposition and to delineate the role of Hg emission and deposition of China in the global Hg biogeochemical cycle, are needed.

Description: A better understanding of hydroxyl radical photochemical sources in cloud waters collected at the puy de Dôme station – experimental versus modelled formation rates Atmospheric Chemistry and Physics, 15, 9191-9202, 2015 Author(s): A. Bianco, M. Passananti, H. Perroux, G. Voyard, C. Mouchel-Vallon, N. Chaumerliac, G. Mailhot, L. Deguillaume, and M. Brigante The oxidative capacity of the cloud aqueous phase is investigated during three field campaigns from 2013 to 2014 at the top of the puy de Dôme station (PUY) in France. A total of 41 cloud samples are collected and the corresponding air masses are classified as highly marine, marine and continental. Hydroxyl radical (HO•) formation rates (R HO• f ) are determined using a photochemical setup (xenon lamp that can reproduce the solar spectrum) and a chemical probe coupled with spectroscopic analysis that can trap all of the generated radicals for each sample. Using this method, the obtained values correspond to the total formation of HO• without its chemical sinks. These formation rates are correlated with the concentrations of the naturally occurring sources of HO•, including hydrogen peroxide, nitrite, nitrate and iron. The total hydroxyl radical formation rates are measured as ranging from approximately 2 × 10 −11 to 4 × 10 −10 M s −1 , and the hydroxyl radical quantum yield formation (Φ HO• ) is estimated between 10 −4 and 10 −2 . Experimental values are compared with modelled formation rates calculated by the model of multiphase cloud chemistry (M2C2), considering only the chemical sources of the hydroxyl radicals. The comparison between the experimental and the modelled results suggests that the photoreactivity of the iron species as a source of HO• is overestimated by the model, and H 2 O 2 photolysis represents the most important source of this radical (between 70 and 99 %) for the cloud water sampled at the PUY station (primarily marine and continental).

Description: Dust–air pollution dynamics over the eastern Mediterranean Atmospheric Chemistry and Physics, 15, 9173-9189, 2015 Author(s): M. Abdelkader, S. Metzger, R. E. Mamouri, M. Astitha, L. Barrie, Z. Levin, and J. Lelieveld Interactions of desert dust and air pollution over the eastern Mediterranean (EM) have been studied, focusing on two distinct dust transport events on 22 and 28 September 2011. The atmospheric chemistry–climate model EMAC has been used at about 50 km grid spacing, applying an online dust emission scheme and calcium as a proxy for dust reactivity. EMAC includes a detailed tropospheric chemistry mechanism, aerosol microphysics and thermodynamics schemes to describe dust "aging". The model is evaluated using ground-based observations for aerosol concentrations and aerosol optical depth (AOD) as well as satellite observations. Simulation results and back trajectory analysis show that the development of synoptic disturbances over the EM can enhance dust transport from the Sahara and Arabian deserts in frontal systems that also carry air pollution to the EM. The frontal systems are associated with precipitation that controls the dust removal. Our results show the importance of chemical aging of dust, which increases particle size, dust deposition and scavenging efficiency during transport, overall reducing the lifetime relative to non-aged dust particles. The relatively long travel periods of Saharan dust result in more sustained aging compared to Arabian dust. Sensitivity simulations indicate 3 times more dust deposition of aged relative to pristine dust, which significantly decreases the dust lifetime and loading.

Description: A method for merging nadir-sounding climate records, with an application to the global-mean stratospheric temperature data sets from SSU and AMSU Atmospheric Chemistry and Physics, 15, 9271-9284, 2015 Author(s): C. McLandress, T. G. Shepherd, A. I. Jonsson, T. von Clarmann, and B. Funke A method is proposed for merging different nadir-sounding climate data records using measurements from high-resolution limb sounders to provide a transfer function between the different nadir measurements. The two nadir-sounding records need not be overlapping so long as the limb-sounding record bridges between them. The method is applied to global-mean stratospheric temperatures from the NOAA Climate Data Records based on the Stratospheric Sounding Unit (SSU) and the Advanced Microwave Sounding Unit-A (AMSU), extending the SSU record forward in time to yield a continuous data set from 1979 to present, and providing a simple framework for extending the SSU record into the future using AMSU. SSU and AMSU are bridged using temperature measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS), which is of high enough vertical resolution to accurately represent the weighting functions of both SSU and AMSU. For this application, a purely statistical approach is not viable since the different nadir channels are not sufficiently linearly independent, statistically speaking. The near-global-mean linear temperature trends for extended SSU for 1980–2012 are −0.63 ± 0.13, −0.71 ± 0.15 and −0.80 ± 0.17 K decade −1 (95 % confidence) for channels 1, 2 and 3, respectively. The extended SSU temperature changes are in good agreement with those from the Microwave Limb Sounder (MLS) on the Aura satellite, with both exhibiting a cooling trend of ~ 0.6 ± 0.3 K decade −1 in the upper stratosphere from 2004 to 2012. The extended SSU record is found to be in agreement with high-top coupled atmosphere–ocean models over the 1980–2012 period, including the continued cooling over the first decade of the 21st century.

Description: Ash iron mobilization through physicochemical processing in volcanic eruption plumes: a numerical modeling approach Atmospheric Chemistry and Physics, 15, 9361-9379, 2015 Author(s): G. A. Hoshyaripour, M. Hort, and B. Langmann It has been shown that volcanic ash fertilizes the Fe-limited areas of the surface ocean through releasing soluble iron. As ash iron is mostly insoluble upon the eruption, it is hypothesized that heterogeneous in-plume and in-cloud processing of the ash promote the iron solubilization. Direct evidences concerning such processes are, however, lacking. In this study, a 1-D numerical model is developed to simulate the physicochemical interactions of the gas–ash–aerosol in volcanic eruption plumes focusing on the iron mobilization processes at temperatures between 600 and 0 °C. Results show that sulfuric acid and water vapor condense at ~ 150 and ~ 50 °C on the ash surface, respectively. This liquid phase then efficiently scavenges the surrounding gases (〉 95 % of HCl, 3–20 % of SO 2 and 12–62 % of HF) forming an extremely acidic coating at the ash surface. The low pH conditions of the aqueous film promote acid-mediated dissolution of the Fe-bearing phases present in the ash material. We estimate that 0.1–33 % of the total iron available at the ash surface is dissolved in the aqueous phase before the freezing point is reached. The efficiency of dissolution is controlled by the halogen content of the erupted gas as well as the mineralogy of the iron at ash surface: elevated halogen concentrations and presence of Fe 2+ -carrying phases lead to the highest dissolution efficiency. Findings of this study are in agreement with the data obtained through leaching experiments.

Description: Methods for automatized detection of rapid changes in lateral boundary condition fields for NWP limited area models Geoscientific Model Development, 8, 2627-2643, 2015 Author(s): M. Tudor Three-hourly temporal resolution of lateral boundary data for limited area models (LAMs) can be too infrequent to resolve rapidly moving storms. This problem is expected to be worse with increasing horizontal resolution. In order to detect intensive disturbances in surface pressure moving rapidly through the model domain, a filtered surface pressure field (MCUF) is computed operationally in the ARPEGE global model of Météo France. The field is distributed in the coupling files along with conventional meteorological fields used for lateral boundary conditions (LBCs) for the operational forecast using limited area model ALADIN (Aire Limitée Adaptation dynamique Développement InterNational) in the Meteorological and Hydrological Service of Croatia (DHMZ). Here an analysis is performed of the MCUF field for the LACE coupling domain for the period from 23 January 2006, when it became available, until 15 November 2014. The MCUF field is a good indicator of rapidly moving pressure disturbances (RMPDs). Its spatial and temporal distribution can be associated with the usual cyclone tracks and areas known to be supporting cyclogenesis. An alternative set of coupling files from the IFS operational run in the European Centre for Medium-Range Weather Forecasts (ECMWF) is also available operationally in DHMZ with 3-hourly temporal resolution, but the MCUF field is not available. Here, several methods are tested that detect RMPDs in surface pressure a posteriori from the IFS model fields provided in the coupling files. MCUF is computed by running ALADIN on the coupling files from IFS. The error function is computed using one-time-step integration of ALADIN on the coupling files without initialization, initialized with digital filter initialization (DFI) or scale-selective DFI (SSDFI). Finally, the amplitude of changes in the mean sea level pressure is computed from the fields in the coupling files. The results are compared to the MCUF field of ARPEGE and the results of same methods applied to the coupling files from ARPEGE. Most methods give a signal for the RMPDs, but DFI reduces the storms too much to be detected. The error functions without filtering and amplitude have more noise, but the signal of a RMPD is also stronger. The methods are tested for NWP LAM ALADIN, but could be applied to other LAMs and benefit the performance of climate LAMs.

Description: Concentrations and solubility of trace elements in fine particles at a mountain site, southern China: regional sources and cloud processing Atmospheric Chemistry and Physics, 15, 8987-9002, 2015 Author(s): T. Li, Y. Wang, W. J. Li, J. M. Chen, T. Wang, and W. X. Wang The concentrations and solubility of twelve trace elements in PM 2.5 at Mt. Lushan, southern China, were investigated during the summer of 2011 and the spring of 2012. The average PM 2.5 mass was 55.2 ± 20.1 μg m −3 during the observation period. Temporal variations of all trace elements including total and water-soluble fractions with several dust storm spikes in total fractions of Al and Fe were observed. The enrichment factor (EF) values were 1 order of magnitude higher for the water-soluble fractions versus the total fractions of trace elements. Four major emission sources, namely nonferrous metal mining and smelting (for Cr, As, Ba and parts of Zn), coal combustion (for Pb, Zn, Se, Cu and Mn), crustal materials (for Al and Fe) and municipal solid waste incineration (for Cd and Mo), were classified by principal component analysis (PCA). Trajectory cluster analysis and the potential source contribution function (PSCF) consistently identified the Yangtze River delta (YRD), the Pearl River delta (PRD), and the neighbouring provinces of Mt. Lushan as the major source regions and transport pathways for anthropogenic elements. Northern China was identified as a major source region for crustal elements. It should be noted that apart from the YRD, the area around Mt. Lushan has become the most significant contributor to the solubility of most trace elements. Element solubility can be partially determined by emission sources. However, enhanced solubility of trace elements corresponding to increased concentrations of sulfate after the occurrence of cloud events indicated significant effects of cloud processing on aerosol element dissolution. Metal particles mixed with sulfate in cloud droplet residues were further investigated through transmission electron microscopy (TEM) analysis. Irreversible alteration of particle morphology by cloud processing was confirmed to be highly responsible for the enhancement of trace element solubility. The findings from this study imply an important role of regional anthropogenic pollution and cloud processing in the evolution of aerosol trace element solubility during transport in the troposphere.

Description: PISCES-v2: an ocean biogeochemical model for carbon and ecosystem studies Geoscientific Model Development, 8, 2465-2513, 2015 Author(s): O. Aumont, C. Ethé, A. Tagliabue, L. Bopp, and M. Gehlen PISCES-v2 (Pelagic Interactions Scheme for Carbon and Ecosystem Studies volume 2) is a biogeochemical model which simulates the lower trophic levels of marine ecosystems (phytoplankton, microzooplankton and mesozooplankton) and the biogeochemical cycles of carbon and of the main nutrients (P, N, Fe, and Si). The model is intended to be used for both regional and global configurations at high or low spatial resolutions as well as for short-term (seasonal, interannual) and long-term (climate change, paleoceanography) analyses. There are 24 prognostic variables (tracers) including two phytoplankton compartments (diatoms and nanophytoplankton), two zooplankton size classes (microzooplankton and mesozooplankton) and a description of the carbonate chemistry. Formulations in PISCES-v2 are based on a mixed Monod–quota formalism. On the one hand, stoichiometry of C / N / P is fixed and growth rate of phytoplankton is limited by the external availability in N, P and Si. On the other hand, the iron and silicon quotas are variable and the growth rate of phytoplankton is limited by the internal availability in Fe. Various parameterizations can be activated in PISCES-v2, setting, for instance, the complexity of iron chemistry or the description of particulate organic materials. So far, PISCES-v2 has been coupled to the Nucleus for European Modelling of the Ocean (NEMO) and Regional Ocean Modeling System (ROMS) systems. A full description of PISCES-v2 and of its optional functionalities is provided here. The results of a quasi-steady-state simulation are presented and evaluated against diverse observational and satellite-derived data. Finally, some of the new functionalities of PISCES-v2 are tested in a series of sensitivity experiments.

Description: Interactions among drainage flows, gravity waves and turbulence: a BLLAST case study Atmospheric Chemistry and Physics, 15, 9031-9047, 2015 Author(s): C. Román-Cascón, C. Yagüe, L. Mahrt, M. Sastre, G.-J. Steeneveld, E. Pardyjak, A. van de Boer, and O. Hartogensis The interactions among several stable-boundary-layer (SBL) processes occurring just after the evening transition of 2 July 2011 have been analysed using data from instruments deployed over the area of Lannemezan (France) during the Boundary Layer Late Afternoon and Sunset Turbulence (BLLAST) field campaign. The near-calm situation of the afternoon was followed by the formation of local shallow drainage flows (SDFs) of less than 10 m depth at different locations. The SDF stage ended with the arrival of a stronger wind over a deeper layer more associated with the mountain-plain circulation, which caused mixing and destruction of the SDFs. Several gravity-wave-related oscillations were also observed on different time series. Wavelet analyses and wave parameters were calculated from high resolution and accurate surface pressure data of an array of microbarometers. These waves propagated relatively long distances within the SBL. The effects of these phenomena on turbulent parameters (friction velocity and kinematic heat flux) have been studied through multi-resolution flux decomposition methods performed on high frequency data from sonic anemometers deployed at different heights and locations. With this method, we were able to detect the different time-scales involved in each turbulent parameter and separate them from wave contributions, which becomes very important when choosing averaging-windows for surface flux computations using eddy covariance methods. The extensive instrumentation allowed us to highlight in detail the peculiarities of the surface turbulent parameters in the SBL, where several of the noted processes were interacting and producing important variations in turbulence with height and between sites along the sloping terrain.

Description: Three-dimensional dust aerosol distribution and extinction climatology over northern Africa simulated with the ALADIN numerical prediction model from 2006 to 2010 Atmospheric Chemistry and Physics, 15, 9063-9082, 2015 Author(s): M. Mokhtari, P. Tulet, C. Fischer, Y. Bouteloup, F. Bouyssel, and O. Brachemi The seasonal cycle and optical properties of mineral dust aerosols in northern Africa were simulated for the period from 2006 to 2010 using the numerical atmospheric model ALADIN (Aire Limitée Adaptation dynamique Développement InterNational) coupled to the surface scheme SURFEX (SURFace EXternalisée). The particularity of the simulations is that the major physical processes responsible for dust emission and transport, as well as radiative effects, are taken into account on short timescales and at mesoscale resolution. The aim of these simulations is to quantify the dust emission and deposition, locate the major areas of dust emission and establish a climatology of aerosol optical properties in northern Africa. The mean monthly aerosol optical thickness (AOT) simulated by ALADIN is compared with the AOTs derived from the standard Dark Target (DT) and Deep Blue (DB) algorithms of the Aqua-MODIS (MODerate resolution Imaging Spectroradiometer) products over northern Africa and with a set of sun photometer measurements located at Banizoumbou, Cinzana, Soroa, Mbour and Cape Verde. The vertical distribution of dust aerosol represented by extinction profiles is also analysed using CALIOP (Cloud-Aerosol Lidar with Orthogonal Polarization) observations. The annual dust emission simulated by ALADIN over northern Africa is 878 Tg year −1 . The Bodélé Depression appears to be the main area of dust emission in northern Africa, with an average estimate of about 21.6 Tg year −1 . The simulated AOTs are in good agreement with satellite and sun photometer observations. The positions of the maxima of the modelled AOTs over northern Africa match the observed positions, and the ALADIN simulations satisfactorily reproduce the various dust events over the 2006–2010 period. The AOT climatology proposed in this paper provides a solid database of optical properties and consolidates the existing climatology over this region derived from satellites, the AERONET network and regional climate models. Moreover, the 3-D distribution of the simulated AOTs also provides information about the vertical structure of the dust aerosol extinction.

Description: On the use of satellite-derived CH 4 : CO 2 columns in a joint inversion of CH 4 and CO 2 fluxes Atmospheric Chemistry and Physics, 15, 8615-8629, 2015 Author(s): S. Pandey, S. Houweling, M. Krol, I. Aben, and T. Röckmann We present a method for assimilating total column CH 4 : CO 2 ratio measurements from satellites for inverse modeling of CH 4 and CO 2 fluxes using the variational approach. Unlike conventional approaches, in which retrieved CH 4 : CO 2 are multiplied by model-derived total column CO 2 and only the resulting CH 4 is assimilated, our method assimilates the ratio of CH 4 and CO 2 directly and is therefore called the ratio method. It is a dual tracer inversion, in which surface fluxes of CH 4 and CO 2 are optimized simultaneously. The optimization of CO 2 fluxes turns the hard constraint of prescribing model-derived CO 2 fields into a weak constraint on CO 2 , which allows us to account for uncertainties in CO 2 . The method has been successfully tested in a synthetic inversion setup. We show that the ratio method is able to reproduce assumed true CH 4 and CO 2 fluxes starting from a prior, which is derived by perturbing the true fluxes randomly. We compare the performance of the ratio method with that of the traditional proxy approach and the use of only surface measurements for estimating CH 4 fluxes. Our results confirm that the optimized CH 4 fluxes are sensitive to the treatment of CO 2 , and that hard constraints on CO 2 may significantly compromise results that are obtained for CH 4 . We find that the relative performance of ratio and proxy methods have a regional dependence. The ratio method performs better than the proxy method in regions where the CO 2 fluxes are most uncertain. However, both ratio and proxy methods perform better than the surface-measurement-only inversion, confirming the potential of spaceborne measurements for accurately determining fluxes of CH 4 and other greenhouse gases (GHGs).

Description: Relationships between photosynthesis and formaldehyde as a probe of isoprene emission Atmospheric Chemistry and Physics, 15, 8559-8576, 2015 Author(s): Y. Zheng, N. Unger, M. P. Barkley, and X. Yue Atmospheric oxidation of isoprene emission from land plants affects radiative forcing of global climate change. There is an urgent need to understand the factors that control isoprene emission variability on large spatiotemporal scales but such direct observations of isoprene emission do not exist. Two readily available global-scale long-term observation-based data sets hold information about surface isoprene activity: gross primary productivity (GPP) and tropospheric formaldehyde column variability (HCHOv). We analyze multi-year seasonal linear correlations between observed GPP and HCHOv. The observed GPP–HCHOv correlation patterns are used to evaluate a global Earth system model that embeds three alternative leaf-level isoprene emission algorithms. GPP and HCHOv are decoupled in the summertime in the southeast US ( r =−0.03). In the Amazon, GPP and HCHOv are weakly correlated in March-April-May (MAM), correlated in June-July-August (JJA) and weakly anticorrelated in September-October-November (SON). Isoprene emission algorithms that include soil moisture dependence demonstrate greater skill in reproducing the observed interannual seasonal GPP–HCHOv correlations in the southeast US and the Amazon. In isoprene emission models that include soil moisture dependence, isoprene emission is correlated with photosynthesis and anticorrelated with HCHOv. In an isoprene emission model without soil moisture dependence, isoprene emission is anticorrelated with photosynthesis and correlated with HCHOv. Long-term monitoring of isoprene emission, soil moisture and meteorology is required in water-limited ecosystems to improve understanding of the factors controlling isoprene emission and its representation in global Earth system models.

Description: Effects of urban land expansion on the regional meteorology and air quality of eastern China Atmospheric Chemistry and Physics, 15, 8597-8614, 2015 Author(s): W. Tao, J. Liu, G. A. Ban-Weiss, D. A. Hauglustaine, L. Zhang, Q. Zhang, Y. Cheng, Y. Yu, and S. Tao Rapid urbanization throughout eastern China is imposing an irreversible effect on local climate and air quality. In this paper, we examine the response of a range of meteorological and air quality indicators to urbanization. Our study uses the Weather Research and Forecasting model coupled with chemistry (WRF/Chem) to simulate the climate and air quality impacts of four hypothetical urbanization scenarios with fixed surface pollutant emissions during the month of July from 2008 to 2012. An improved integrated process rate (IPR) analysis scheme is implemented in WRF/Chem to investigate the mechanisms behind the forcing–response relationship at the process level. For all years, as urban land area expands, concentrations of CO, elemental carbon (EC), and particulate matter with aerodynamic diameter less than 2.5 microns (PM 2.5 ) tend to decrease near the surface (below ~ 500 m), but increase at higher altitudes (1–3 km), resulting in a reduced vertical concentration gradient. On the other hand, the O 3 burden, averaged over all newly urbanized grid cells, consistently increases from the surface to a height of about 4 km. Sensitivity tests show that the responses of pollutant concentrations to the spatial extent of urbanization are nearly linear near the surface, but nonlinear at higher altitudes. Over eastern China, each 10 % increase in nearby urban land coverage on average leads to a decrease of approximately 2 % in surface concentrations for CO, EC, and PM 2.5 , while for O 3 an increase of about 1 % is simulated. At 800 hPa, pollutants' concentrations tend to increase even more rapidly with an increase in nearby urban land coverage. This indicates that as large tracts of new urban land emerge, the influence of urban expansion on meteorology and air pollution would be significantly amplified. IPR analysis reveals the contribution of individual atmospheric processes to pollutants' concentration changes. It indicates that, for primary pollutants, the enhanced sink (source) caused by turbulent mixing and vertical advection in the lower (upper) atmosphere could be a key factor in changes to simulated vertical profiles. The evolution of secondary pollutants is further influenced by the upward relocation of precursors that impact gas-phase chemistry for O 3 and aerosol processes for PM 2.5 . Our study indicates that dense urbanization has a moderate dilution effect on surface primary airborne contaminants, but may intensify severe haze and ozone pollution if local emissions are not well controlled.

Description: Improvement of climate predictions and reduction of their uncertainties using learning algorithms Atmospheric Chemistry and Physics, 15, 8631-8641, 2015 Author(s): E. Strobach and G. Bel Simulated climate dynamics, initialized with observed conditions, is expected to be synchronized, for several years, with the actual dynamics. However, the predictions of climate models are not sufficiently accurate. Moreover, there is a large variance between simulations initialized at different times and between different models. One way to improve climate predictions and to reduce the associated uncertainties is to use an ensemble of climate model predictions, weighted according to their past performances. Here, we show that skillful predictions, for a decadal time scale, of the 2 m temperature can be achieved by applying a sequential learning algorithm to an ensemble of decadal climate model simulations. The predictions generated by the learning algorithm are shown to be better than those of each of the models in the ensemble, the better performing simple average and a reference climatology. In addition, the uncertainties associated with the predictions are shown to be reduced relative to those derived from an equally weighted ensemble of bias-corrected predictions. The results show that learning algorithms can help to better assess future climate dynamics.

Description: Carbon isotopes in the ocean model of the Community Earth System Model (CESM1) Geoscientific Model Development, 8, 2419-2434, 2015 Author(s): A. Jahn, K. Lindsay, X. Giraud, N. Gruber, B. L. Otto-Bliesner, Z. Liu, and E. C. Brady Carbon isotopes in the ocean are frequently used as paleoclimate proxies and as present-day geochemical ocean tracers. In order to allow a more direct comparison of climate model results with this large and currently underutilized data set, we added a carbon isotope module to the ocean model of the Community Earth System Model (CESM), containing the cycling of the stable isotope 13 C and the radioactive isotope 14 C. We implemented the 14 C tracer in two ways: in the "abiotic" case, the 14 C tracer is only subject to air–sea gas exchange, physical transport, and radioactive decay, while in the "biotic" version, the 14 C additionally follows the 13 C tracer through all biogeochemical and ecological processes. Thus, the abiotic 14 C tracer can be run without the ecosystem module, requiring significantly fewer computational resources. The carbon isotope module calculates the carbon isotopic fractionation during gas exchange, photosynthesis, and calcium carbonate formation, while any subsequent biological process such as remineralization as well as any external inputs are assumed to occur without fractionation. Given the uncertainty associated with the biological fractionation during photosynthesis, we implemented and tested three parameterizations of different complexity. Compared to present-day observations, the model is able to simulate the oceanic 14 C bomb uptake and the 13 C Suess effect reasonably well compared to observations and other model studies. At the same time, the carbon isotopes reveal biases in the physical model, for example, too sluggish ventilation of the deep Pacific Ocean.

Description: Revision of the convective transport module CVTRANS 2.4 in the EMAC atmospheric chemistry–climate model Geoscientific Model Development, 8, 2435-2445, 2015 Author(s): H. G. Ouwersloot, A. Pozzer, B. Steil, H. Tost, and J. Lelieveld The convective transport module, CVTRANS, of the ECHAM/MESSy Atmospheric Chemistry (EMAC) model has been revised to better represent the physical flows and incorporate recent findings on the properties of the convective plumes. The modifications involve (i) applying intermediate time stepping based on a settable criterion, (ii) using an analytic expression to account for the intra-time-step mixing ratio evolution below cloud base, and (iii) implementing a novel expression for the mixing ratios of atmospheric compounds at the base of an updraft. Even when averaged over a year, the predicted mixing ratios of atmospheric compounds are affected considerably by the intermediate time stepping. For example, for an exponentially decaying atmospheric tracer with a lifetime of 1 day, the zonal averages can locally differ by more than a factor of 6 and the induced root mean square deviation from the original code is, weighted by the air mass, higher than 40 % of the average mixing ratio. The other modifications result in smaller differences. However, since they do not require additional computational time, their application is also recommended.

Description: On the link between hygroscopicity, volatility, and oxidation state of ambient and water-soluble aerosols in the southeastern United States Atmospheric Chemistry and Physics, 15, 8679-8694, 2015 Author(s): K. M. Cerully, A. Bougiatioti, J. R. Hite Jr., H. Guo, L. Xu, N. L. Ng, R. Weber, and A. Nenes The formation of secondary organic aerosols (SOAs) combined with the partitioning of semivolatile organic components can impact numerous aerosol properties including cloud condensation nuclei (CCN) activity, hygroscopicity, and volatility. During the summer 2013 Southern Oxidant and Aerosol Study (SOAS) field campaign in a rural site in the southeastern United States, a suite of instruments including a CCN counter, a thermodenuder (TD), and a high-resolution time-of-flight aerosol mass spectrometer (AMS) were used to measure CCN activity, aerosol volatility, composition, and oxidation state. Particles were either sampled directly from ambient or through a particle-into-liquid sampler (PILS), allowing the investigation of the water-soluble aerosol component. Ambient aerosols exhibited size-dependent composition with larger particles being more hygroscopic. The hygroscopicity of thermally denuded aerosols was similar between ambient and PILS-generated aerosols and showed limited dependence on volatilization. Results of AMS three-factor positive matrix factorization (PMF) analysis for the PILS-generated aerosols showed that the most hygroscopic components are most likely the most and the least volatile features of the aerosols. No clear relationship was found between organic hygroscopicity and the oxygen-to-carbon ratio; in fact, isoprene-derived organic aerosols (isoprene-OAs) were found to be the most hygroscopic factor, while at the same time being the least oxidized and likely most volatile of all PMF factors. Considering the diurnal variation of each PMF factor and its associated hygroscopicity, isoprene-OA and more-oxidized oxygenated organic aerosols are the prime contributors to hygroscopicity and co-vary with less-oxidized oxygenated organic aerosols in a way that induces the observed diurnal invariance in total organic hygroscopicity. Biomass burning organic aerosols contributed little to aerosol hygroscopicity, which is expected since there was little biomass burning activity during the sampling period examined.

Description: Vertical resolution dependence of gravity wave momentum flux simulated by an atmospheric general circulation model Geoscientific Model Development, 8, 1637-1644, 2015 Author(s): S. Watanabe, K. Sato, Y. Kawatani, and M. Takahashi The dependence of the gravity wave spectra of energy and momentum flux on the horizontal resolution and time step of atmospheric general circulation models (AGCMs) has been thoroughly investigated in the past. In contrast, much less attention has been given to the dependence of these gravity wave parameters on models' vertical resolutions. The present study demonstrates the dependence of gravity wave momentum flux (GWMF) in the stratosphere and mesosphere on the model's vertical resolution, which is evaluated using an AGCM with a horizontal resolution of about 0.56°. We performed a series of sensitivity test simulations changing only the model's vertical resolution above a height of 8 km, and found a global reduction of GWMF with increasing vertical resolution. Inertial gravity waves with short vertical wavelengths simulated at higher vertical resolutions might play an important role in determining GWMF in the summertime stratosphere. The sensitivity test simulation also demonstrated the importance of the model's vertical resolution on representing realistic behaviors of gravity waves near their critical level.

Description: Mass-conserving subglacial hydrology in the Parallel Ice Sheet Model version 0.6 Geoscientific Model Development, 8, 1613-1635, 2015 Author(s): E. Bueler and W. van Pelt We describe and test a two-horizontal-dimension subglacial hydrology model which combines till with a distributed system of water-filled, linked cavities which open through sliding and close through ice creep. The addition of this sub-model to the Parallel Ice Sheet Model (PISM) accomplishes three specific goals: (a) conservation of the mass of water, (b) simulation of spatially and temporally variable basal shear stress from physical mechanisms based on a minimal number of free parameters, and (c) convergence under grid refinement. The model is a common generalization of four others: (i) the undrained plastic bed model of Tulaczyk et al. (2000b), (ii) a standard "routing" model used for identifying locations of subglacial lakes, (iii) the lumped englacial–subglacial model of Bartholomaus et al. (2011), and (iv) the elliptic-pressure-equation model of Schoof et al. (2012). We preserve physical bounds on the pressure. In steady state a functional relationship between water amount and pressure emerges. We construct an exact solution of the coupled, steady equations and use it for verification of our explicit time stepping, parallel numerical implementation. We demonstrate the model at scale by 5 year simulations of the entire Greenland ice sheet at 2 km horizontal resolution, with one million nodes in the hydrology grid.

Description: ICON–ART 1.0 – a new online-coupled model system from the global to regional scale Geoscientific Model Development, 8, 1659-1676, 2015 Author(s): D. Rieger, M. Bangert, I. Bischoff-Gauss, J. Förstner, K. Lundgren, D. Reinert, J. Schröter, H. Vogel, G. Zängl, R. Ruhnke, and B. Vogel We present the first stage of a new online-coupled global to regional-scale modeling framework for the simulation of the spatiotemporal evolution of aerosols and trace gases. The underlying meteorological model is the new nonhydrostatic model system ICON (ICOsahedral Nonhydrostatic) which allows a local grid refinement with two-way interactions between the grids. We develop the extension ART (Aerosol and Reactive Trace gases) with the goal of simulating interactions between trace substances and the state of the atmosphere. Within this paper, we present the basic equations and give an overview of the physical parameterizations as well as numerical methods we use. First applications of the new model system for trace gases, monodisperse particles and polydisperse particles are shown. The simulated distribution of two very short-lived substances (VSLS), bromoform (CHBr 3 ) and dibromomethane (CH 2 Br 2 ) reflecting the fast upward transport shows a good agreement with observations and previous model studies. Also, the shape of the simulated tropical profiles is well reproduced. As an example for the treatment of monodisperse particles we present the simulated ash plume of the Eyjafjallajökull eruption in April 2010. Here, a novel approach for the source function is applied. The pattern of the simulated distribution of volcanic ash particles shows a good agreement with previous studies. As an example for the treatment of a polydisperse aerosol, where number densities and mass concentrations are accounted for, we simulated the annual emissions of sea salt. We obtain a total emission flux of 26.0 Pg yr −1 and an emission flux of particles with diameter less than 10 μm of 7.36 Pg yr −1 .

Description: Regional-scale simulations of fungal spore aerosols using an emission parameterization adapted to local measurements of fluorescent biological aerosol particles Atmospheric Chemistry and Physics, 15, 6127-6146, 2015 Author(s): M. Hummel, C. Hoose, M. Gallagher, D. A. Healy, J. A. Huffman, D. O'Connor, U. Pöschl, C. Pöhlker, N. H. Robinson, M. Schnaiter, J. R. Sodeau, M. Stengel, E. Toprak, and H. Vogel Fungal spores as a prominent type of primary biological aerosol particles (PBAP) have been incorporated into the COSMO-ART (Consortium for Small-scale Modelling-Aerosols and Reactive Trace gases) regional atmospheric model. Two literature-based emission rates for fungal spores derived from fungal spore colony counts and chemical tracer measurements were used as a parameterization baseline for this study. A third, new emission parameterization for fluorescent biological aerosol particles (FBAP) was adapted to field measurements from four locations across Europe. FBAP concentrations can be regarded as a lower estimate of total PBAP concentrations. Size distributions of FBAP often show a distinct mode at approx. 3 μm, corresponding to a diameter range characteristic for many fungal spores. Previous studies for several locations have suggested that FBAP are in many cases dominated by fungal spores. Thus, we suggest that simulated FBAP and fungal spore concentrations obtained from the three different emission parameterizations can be compared to FBAP measurements. The comparison reveals that simulated fungal spore concentrations based on literature emission parameterizations are lower than measured FBAP concentrations. In agreement with the measurements, the model results show a diurnal cycle in simulated fungal spore concentrations, which may develop partially as a consequence of a varying boundary layer height between day and night. Temperature and specific humidity, together with leaf area index (LAI), were chosen to drive the new emission parameterization which is fitted to the FBAP observations. The new parameterization results in similar root mean square errors (RMSEs) and correlation coefficients compared to the FBAP observations as the previously existing fungal spore emission parameterizations, with some improvements in the bias. Using the new emission parameterization on a model domain covering western Europe, FBAP in the lowest model layer comprise a fraction of 15% of the total aerosol mass over land and reach average number concentrations of 26 L −1 . The results confirm that fungal spores and biological particles may account for a major fraction of supermicron aerosol particle number and mass concentration over vegetated continental regions and should thus be explicitly considered in air quality and climate studies.

Description: Photochemical processing of aqueous atmospheric brown carbon Atmospheric Chemistry and Physics, 15, 6087-6100, 2015 Author(s): R. Zhao, A. K. Y. Lee, L. Huang, X. Li, F. Yang, and J. P. D. Abbatt Atmospheric brown carbon (BrC) is a collective term for light absorbing organic compounds in the atmosphere. While the identification of BrC and its formation mechanisms is currently a central effort in the community, little is known about the atmospheric removal processes of aerosol BrC. As a result, we report on a series of laboratory studies of photochemical processing of BrC in the aqueous phase, by direct photolysis and OH oxidation. Solutions of ammonium sulfate mixed with glyoxal (GLYAS) or methylglyoxal (MGAS) are used as surrogates for a class of secondary BrC mediated by imine intermediates. Three nitrophenol species, namely 4-nitrophenol, 5-nitroguaiacol and 4-nitrocatechol, were investigated as a class of water-soluble BrC originating from biomass burning. Photochemical processing induced significant changes in the absorptive properties of BrC. The imine-mediated BrC solutions exhibited rapid photo-bleaching with both direct photolysis and OH oxidation, with atmospheric half-lives of minutes to a few hours. The nitrophenol species exhibited photo-enhancement in the visible range during direct photolysis and the onset of OH oxidation, but rapid photo-bleaching was induced by further OH exposure on an atmospheric timescale of an hour or less. To illustrate the atmospheric relevance of this work, we also performed direct photolysis experiments on water-soluble organic carbon extracted from biofuel combustion samples and observed rapid changes in the optical properties of these samples as well. Overall, these experiments indicate that atmospheric models need to incorporate representations of atmospheric processing of BrC species to accurately model their radiative impacts.

Description: Ozone and aerosol tropospheric concentrations variability analyzed using the ADRIMED measurements and the WRF and CHIMERE models Atmospheric Chemistry and Physics, 15, 6159-6182, 2015 Author(s): L. Menut, S. Mailler, G. Siour, B. Bessagnet, S. Turquety, G. Rea, R. Briant, M. Mallet, J. Sciare, P. Formenti, and F. Meleux During the months of June and July 2013, over the Euro–Mediterranean area, the ADRIMED (Aerosol Direct Radiative Impact on the regional climate in the MEDiterranean region) project was dedicated to characterize the ozone and aerosol concentrations in the troposphere. It is first shown that this period was not highly polluted compared to previous summers in this region, with a moderate ozone production, no significant vegetation fire events and several precipitation periods scavenging the aerosol. The period is modeled with the WRF (Weather Research and Forecasting) and CHIMERE models, and their ability to quantify the observed pollution transport events is presented. The CHIMERE model simulating all kinds of sources (anthropogenic, biogenic, mineral dust, vegetation fires); the aerosol speciation, not available with the measurements, is presented: during the whole period, the aerosol was mainly constituted by mineral dust, sea salt and sulfates close to the surface and mainly by mineral dust in the troposphere. Compared to the AERONET (Aerosol Robotic Network) size distribution, it is shown that the model underestimates the coarse mode near mineral dust sources and overestimates the fine mode in the Mediterranean area, highlighting the need to improve the model representation of the aerosol size distribution both during emissions, long-range transport and deposition.

Description: Arctic microbial and next-generation sequencing approach for bacteria in snow and frost flowers: selected identification, abundance and freezing nucleation Atmospheric Chemistry and Physics, 15, 6183-6204, 2015 Author(s): R. Mortazavi, S. Attiya, and P. A. Ariya During the spring of 2009, as part of the Ocean–Atmosphere–Sea Ice–Snowpack (OASIS) campaign in Barrow, Alaska, USA, we examined the identity, population diversity, freezing nucleation ability of the microbial communities of five different snow types and frost flowers. In addition to the culturing and gene-sequence-based identification approach, we utilized a state-of-the-art genomic next-generation sequencing (NGS) technique to examine the diversity of bacterial communities in Arctic samples. Known phyla or candidate divisions were detected (11–18) with the majority of sequences (12.3–83.1%) belonging to one of the five major phyla: Proteobacteria, Actinobacteria, Bacteroidetes, Firmicutes, and Cyanobacteria. The number of genera detected ranged from, 101–245. The highest number of cultivable bacteria was observed in frost flowers (FFs) and accumulated snow (AS) with 325 ± 35 and 314 ± 142 CFU m L −1 , respectively; and for cultivable fungi 5 ± 1 CFU m L −1 in windpack (WP) and blowing snow (BS). Morphology/elemental composition and ice-nucleating abilities of the identified taxa were obtained using high resolution electron microscopy with energy-dispersive X-ray spectroscopy and ice nucleation cold-plate, respectively. Freezing point temperatures for bacterial isolates ranged from −20.3 ± 1.5 to −15.7 ± 5.6 °C, and for melted snow samples from −9.5 ± 1.0 to −18.4 ± 0.1 °C. An isolate belonging to the genus Bacillus (96% similarity) had ice nucleation activity of −6.8 ± 0.2 °C. Comparison with Montreal urban snow, revealed that a seemingly diverse community of bacteria exists in the Arctic with some taxa possibly originating from distinct ecological environments. We discuss the potential impact of snow microorganisms in the freezing and melting process of the snowpack in the Arctic.

Description: Corrigendum to "In situ vertical profiles of aerosol extinction, mass, and composition over the southeast United States during SENEX and SEAC 4 RS: observations of a modest aerosol enhancement aloft" published in Atmos. Chem. Phys., 15, 7085–7102, 2015 Atmospheric Chemistry and Physics, 15, 8455-8455, 2015 Author(s): N. L. Wagner, C. A. Brock, W. M. Angevine, A. Beyersdorf, P. Campuzano-Jost, D. A. Day, J. A. de Gouw, G. S. Diskin, T. D. Gordon, M. G. Graus, J. S. Holloway, G. Huey, J. L. Jimenez, D. A. Lack, J. Liao, X. Liu, M. Z. Markovic, A. M. Middlebrook, T. Mikoviny, J. Peischl, A. E. Perring, M. S. Richardson, T. B. Ryerson, J. P. Schwarz, C. Warneke, A. Welti, A. Wisthaler, L. D. Ziemba, and D. M. Murphy No abstract available.

Description: X-ray computed microtomography of sea ice – comment on "A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow" by Bartels-Rausch et al. (2014) Atmospheric Chemistry and Physics, 15, 8457-8458, 2015 Author(s): R. W. Obbard This comment addresses a statement made in "A review of air–ice chemical and physical interactions (AICI): liquids, quasi-liquids, and solids in snow" by Bartels-Rausch et al. (Atmos. Chem. Phys., 14, 1587–1633, doi:10.5194/acp-14-1587-2014 , 2014). Here we rebut the assertion that X-ray computed microtomography of sea ice fails to reveal liquid brine inclusions by discussing the phases present at the analysis temperature.

Description: An observation-constrained multi-physics WRF ensemble for simulating European mega heat waves Geoscientific Model Development, 8, 2285-2298, 2015 Author(s): A. I. Stegehuis, R. Vautard, P. Ciais, A. J. Teuling, D. G. Miralles, and M. Wild Many climate models have difficulties in properly reproducing climate extremes, such as heat wave conditions. Here we use the Weather Research and Forecasting (WRF) regional climate model with a large combination of different atmospheric physics schemes, in combination with the NOAH land-surface scheme, with the goal of detecting the most sensitive physics and identifying those that appear most suitable for simulating the heat wave events of 2003 in western Europe and 2010 in Russia. In total, 55 out of 216 simulations combining different atmospheric physical schemes have a temperature bias smaller than 1 °C during the heat wave episodes, the majority of simulations showing a cold bias of on average 2–3 °C. Conversely, precipitation is mostly overestimated prior to heat waves, and shortwave radiation is slightly overestimated. Convection is found to be the most sensitive atmospheric physical process impacting simulated heat wave temperature across four different convection schemes in the simulation ensemble. Based on these comparisons, we design a reduced ensemble of five well performing and diverse scheme configurations, which may be used in the future to perform heat wave analysis and to investigate the impact of climate change during summer in Europe.

Description: Contribution from biogenic organic compounds to particle growth during the 2010 BEACHON-ROCS campaign in a Colorado temperate needleleaf forest Atmospheric Chemistry and Physics, 15, 8643-8656, 2015 Author(s): L. Zhou, R. Gierens, A. Sogachev, D. Mogensen, J. Ortega, J. N. Smith, P. C. Harley, A. J. Prenni, E. J. T. Levin, A. Turnipseed, A. Rusanen, S. Smolander, A. B. Guenther, M. Kulmala, T. Karl, and M. Boy New particle formation (NPF) is an important atmospheric phenomenon. During an NPF event, particles first form by nucleation and then grow further in size. The growth step is crucial because it controls the number of particles that can become cloud condensation nuclei. Among various physical and chemical processes contributing to particle growth, condensation by organic vapors has been suggested as important. In order to better understand the influence of biogenic emissions on particle growth, we carried out modeling studies of NPF events during the BEACHON-ROCS (Bio–hydro–atmosphere interactions of Energy, Aerosol, Carbon, H2O, Organics & Nitrogen – Rocky Mountain Organic Carbon Study) campaign at Manitou Experimental Forest Observatory in Colorado, USA. The site is representative of the semi-arid western USA. With the latest Criegee intermediate reaction rates implemented in the chemistry scheme, the model underestimates sulfuric acid concentration by 50 %, suggesting either missing sources of atmospheric sulfuric acid or an overestimated sink term. The results emphasize the contribution from biogenic volatile organic compound emissions to particle growth by demonstrating the effects of the oxidation products of monoterpenes and 2-Methyl-3-buten-2-ol (MBO). Monoterpene oxidation products are shown to influence the nighttime particle loadings significantly, while their concentrations are insufficient to grow the particles during the day. The growth of ultrafine particles in the daytime appears to be closely related to the OH oxidation products of MBO.

Description: PLUME-MoM 1.0: A new integral model of volcanic plumes based on the method of moments Geoscientific Model Development, 8, 2447-2463, 2015 Author(s): M. de' Michieli Vitturi, A. Neri, and S. Barsotti In this paper a new integral mathematical model for volcanic plumes, named PLUME-MoM, is presented. The model describes the steady-state dynamics of a plume in a 3-D coordinate system, accounting for continuous variability in particle size distribution of the pyroclastic mixture ejected at the vent. Volcanic plumes are composed of pyroclastic particles of many different sizes ranging from a few microns up to several centimeters and more. A proper description of such a multi-particle nature is crucial when quantifying changes in grain-size distribution along the plume and, therefore, for better characterization of source conditions of ash dispersal models. The new model is based on the method of moments, which allows for a description of the pyroclastic mixture dynamics not only in the spatial domain but also in the space of parameters of the continuous size distribution of the particles. This is achieved by formulation of fundamental transport equations for the multi-particle mixture with respect to the different moments of the grain-size distribution. Different formulations, in terms of the distribution of the particle number, as well as of the mass distribution expressed in terms of the Krumbein log scale, are also derived. Comparison between the new moments-based formulation and the classical approach, based on the discretization of the mixture in N discrete phases, shows that the new model allows for the same results to be obtained with a significantly lower computational cost (particularly when a large number of discrete phases is adopted). Application of the new model, coupled with uncertainty quantification and global sensitivity analyses, enables the investigation of the response of four key output variables (mean and standard deviation of the grain-size distribution at the top of the plume, plume height and amount of mass lost by the plume during the ascent) to changes in the main input parameters (mean and standard deviation) characterizing the pyroclastic mixture at the base of the plume. Results show that, for the range of parameters investigated and without considering interparticle processes such as aggregation or comminution, the grain-size distribution at the top of the plume is remarkably similar to that at the base and that the plume height is only weakly affected by the parameters of the grain distribution. The adopted approach can be potentially extended to the consideration of key particle–particle effects occurring in the plume including particle aggregation and fragmentation.

Description: Chemical composition, microstructure, and hygroscopic properties of aerosol particles at the Zotino Tall Tower Observatory (ZOTTO), Siberia, during a summer campaign Atmospheric Chemistry and Physics, 15, 8847-8869, 2015 Author(s): E. F. Mikhailov, G. N. Mironov, C. Pöhlker, X. Chi, M. L. Krüger, M. Shiraiwa, J.-D. Förster, U. Pöschl, S. S. Vlasenko, T. I. Ryshkevich, M. Weigand, A. L. D. Kilcoyne, and M. O. Andreae In this study we describe the hygroscopic properties of accumulation- and coarse-mode aerosol particles sampled at the Zotino Tall Tower Observatory (ZOTTO) in central Siberia (61° N, 89° E) from 16 to 21 June 2013. The hygroscopic growth measurements were supplemented with chemical analyses of the samples, including inorganic ions and organic/elemental carbon. In addition, the microstructure and chemical compositions of aerosol particles were analyzed by x-ray micro-spectroscopy (STXM-NEXAFS) and transmission electron microscopy (TEM). A mass closure analysis indicates that organic carbon accounted for 61 and 38 % of particulate matter (PM) in the accumulation mode and coarse mode, respectively. The water-soluble fraction of organic matter was estimated to be 52 and 8 % of PM in these modes. Sulfate, predominantly in the form of ammoniated sulfate, was the dominant inorganic component in both size modes: ~ 34 % in the accumulation mode vs. ~ 47 % in the coarse mode. The hygroscopic growth measurements were conducted with a filter-based differential hygroscopicity analyzer (FDHA) over the range of 5–99.4 % RH in the hydration and dehydration operation modes. The FDHA study indicates that both accumulation and coarse modes exhibit pronounced water uptake approximately at the same relative humidity (RH), starting at ~ 70 %, while efflorescence occurred at different humidities, i.e., at ~ 35 % RH for submicron particles vs. ~ 50 % RH for supermicron particles. This ~ 15 % RH difference was attributed to higher content of organic material in the submicron particles, which suppresses water release in the dehydration experiments. The kappa mass interaction model (KIM) was applied to characterize and parameterize non-ideal solution behavior and concentration-dependent water uptake by atmospheric aerosol samples in the 5–99.4 % RH range. Based on KIM, the volume-based hygroscopicity parameter, κ v , was calculated. The κ v,ws value related to the water-soluble (ws) fraction was estimated to be ~ 0.15 for the accumulation mode and ~ 0.36 for the coarse mode, respectively. The obtained κ v,ws for the accumulation mode is in good agreement with earlier data reported for remote sites in the Amazon rain forest (κ v ≈ 0.15) and a Colorado mountain forest (κ v ≈ 0.16 ). We used the Zdanovskii–Stokes–Robinson (ZSR) mixing rule to predict the chemical composition dependent hygroscopicity, κ v,p . The obtained κ v,p values overestimate the experimental FDHA-KIM-derived κ v,ws by factors of 1.8 and 1.5 for the accumulation and coarse modes, respectively. This divergence can be explained by incomplete dissolution of the hygroscopic inorganic compounds resulting from kinetic limitations due to a sparingly soluble organic coating. The TEM and STXM-NEXAFS results indicate that aged submicron (〉 300 nm) and supermicron aerosol particles possess core–shell structures with an inorganic core, and are enriched in organic carbon at the mixed particle surface. The direct FDHA kinetic studies provide a bulk diffusion coefficient of water of ~ 10 −12 cm 2 s −1 indicating a semi-solid state of the organic-rich phase leading to kinetic limitations of water uptake and release during hydration and dehydration cycles. Overall, the present ZOTTO data set, obtained in the growing season, has revealed a strong influence of organic carbon on the hygroscopic properties of the ambient aerosols. The sparingly soluble organic coating controls hygroscopic growth, phase transitions, and microstructural rearrangement processes. The observed kinetic limitations can strongly influence the outcome of experiments performed on multi-second timescales, such as the commonly applied HTDMA (Hygroscopicity Tandem Differential Mobility Analyzer) and CCNC (Cloud Condensation Nuclei Counter) measurements.

Description: Hygroscopic and phase separation properties of ammonium sulfate/organics/water ternary solutions Atmospheric Chemistry and Physics, 15, 8975-8986, 2015 Author(s): M. A. Zawadowicz, S. R. Proud, S. S. Seppalainen, and D. J. Cziczo Atmospheric aerosol particles are often partially or completely composed of inorganic salts, such as ammonium sulfate and sodium chloride, and therefore exhibit hygroscopic properties. Many inorganic salts have well-defined deliquescence and efflorescence points at which they take up and lose water, respectively. Field measurements have shown that atmospheric aerosols are not typically pure inorganic salt, instead, they often also contain organic species. There is ample evidence from laboratory studies that suggests that mixed particles exist in a phase-separated state, with an aqueous inorganic core and organic shell. Although phase separation has not been measured in situ, there is no reason it would not also take place in the atmosphere. Here, we investigate the deliquescence and efflorescence points, phase separation and ability to exchange gas-phase components of mixed organic and inorganic aerosol using a flow tube coupled with FTIR (Fourier transform infrared) spectroscopy. Ammonium sulfate aerosol mixed with organic polyols with different O : C ratios, including 1,4-butanediol, glycerol, 1,2,6-hexanetriol, 1,2-hexanediol, and 1,5-pentanediol have been investigated. Those constituents correspond to materials found in the atmosphere in great abundance and, therefore, particles prepared in this study should mimic atmospheric mixed-phase aerosol particles. Some results of this study tend to be in agreement with previous microscopy experiments, but others, such as phase separation properties of 1,2,6-hexanetriol, do not agree with previous work. Because the particles studied in this experiment are of a smaller size than those used in microscopy studies, the discrepancies found could be a size-related effect.