ALBERT

Description: Imperfect scaling in distributions of radar-derived rainfall fields Hydrology and Earth System Sciences Discussions, 10, 11385-11422, 2013 Author(s): M. J. van den Berg, L. Delobbe, and N. E. C. Verhoest Fine scale rainfall observations for modeling exercises are often not available, but rather coarser data derived from a variety of sources are used. Effectively using these data sources in models often requires the probability distribution of the data at the applicable scale. Although numerous models for scaling distributions exist, these are often based on theoretical developments, rather than on data. In this study, we develop a model based on the α-stable distribution of rainfall fields, and tested on 5 min radar data from a Belgian weather radar. We use these data to estimate functions that describe parameters of the distribution over various scales. Moreover, we study how the mean of the distribution and the intermittency change with scale, and validate and design functions to describe the shape parameter of the distribution. This information was combined into an effective model of the distribution. Finally, the model was fitted to data from numerous storms, and the resulting parameters were compared to investigate the change in scaling behavior through time.

Description: Spatially resolved information on karst conduit flow from in-cave dye-tracing Hydrology and Earth System Sciences Discussions, 10, 11311-11335, 2013 Author(s): U. Lauber, W. Ufrecht, and N. Goldscheider Artificial tracers are powerful tools to investigate karst systems. Tracers are commonly injected into sinking streams or dolines, while springs serve as monitoring sites. The obtained flow and transport parameters represent mixed information from the vadose, epiphreatic and phreatic zones, i.e., the aquifer remains a black box. Accessible active caves constitute valuable but underexploited natural laboratories to gain detailed insights into the hydrologic functioning of the aquifer. Two multi-tracer tests in the catchment of a major karst spring (Blautopf, Germany) with injections and monitoring in two associated water caves aimed at obtaining spatially and temporally resolved information on groundwater flow in different compartments of the system. Two tracers were injected in the caves to characterize the hydraulic connections between them and with the spring. Two injections at the land surface, far from the spring, aimed at resolving the aquifer's internal drainage structure. Tracer breakthrough curves were monitored by field fluorimeters in caves and at the spring. Results demonstrate the dendritic drainage structure of the aquifer. It was possible to obtain relevant flow and transport parameters for different sections of this system. The highest mean flow velocities (275 m h −1 ) were observed in the near-spring epiphreatic section (open-channel flow), while velocities in the phreatic zone (pressurized flow) were one order of magnitude lower. Determined conduit water volumes confirm results of water balances and hydrograph analyses. In conclusion, experiments and monitoring in caves can deliver spatially resolved information on karst aquifer heterogeneity and dynamics that cannot be obtained by traditional investigative methods.

Description: On the lack of robustness of hydrologic models regarding water balance simulation – a diagnostic approach on 20 mountainous catchments using three models of increasing complexity Hydrology and Earth System Sciences Discussions, 10, 11337-11383, 2013 Author(s): L. Coron, V. Andréassian, C. Perrin, M. Bourqui, and F. Hendrickx This paper investigates the robustness of rainfall–runoff models when their parameters are transferred in time. More specifically, we studied their ability to simulate water balance on periods with different hydroclimatic characteristics. The testing procedure consisted in a series of parameter transfers between 10-yr periods and the systematic analysis of mean-volume errors. This procedure was applied to three conceptual models of different structural complexity over 20 mountainous catchments in southern France. The results showed that robustness problems are common. Errors on 10-yr-mean flows were significant for all three models and calibration periods, even when the entire record was used for calibration. Various graphical and numerical tools were used to show strong similarities between the shapes of mean flow biases calculated on a 10-yr-long sliding window when various parameter sets are used. Unexpected behavioural similarities were observed between the three models tested, considering their large differences in structural complexity. While the actual causes for robustness problems in these models remain unclear, this work stresses the limited transferability in time of the water balance adjustments made through parameter optimization. Although absolute differences between simulations obtained with different calibrated parameter sets were sometimes substantial, relative differences in simulated mean flows between time periods remained similar regardless of the calibrated parameter sets.

Description: The sensitivity of global climate to the episodicity of fire aerosol emissions Atmospheric Chemistry and Physics Discussions, 13, 23691-23717, 2013 Author(s): S. K. Clark, D. S. Ward, and N. M. Mahowald One of the major ways in which forest and grass fires have an impact on global climate is through the release of aerosols. Most studies focusing on calculating the radiative forcing and other climate impacts of fire aerosols use monthly mean emissions derived from the Global Fire Emissions Database that captures only the seasonal cycle of fire aerosol emissions. Here we present the results of a sensitivity study that investigates the climate response to the episodicity of the fires, based on the standard approach which releases emissions every day, and contrasts that to the response when fires are represented as intense pulses of emissions that occur only over 1–2 days on a monthly, yearly, or five-yearly basis. Overall we find that in the modified cases with increased levels of episodicity, the all sky direct effect radiative forcing increases, the clear sky direct effect radiative forcing remains relatively constant, and the magnitude of the indirect effect radiative forcing decreases by about 1 W m −2 (from −1.6 to −0.6 W m −2 ). In the long term, we find that an increase in aerosol emission episodicity leads to an asymmetric change in indirect radiative forcing in the Northern Hemisphere compared to the Southern Hemisphere contributes to a slight shift in the annual average position of the intertropical convergence zone (ITCZ). This shift is found to have a mixed effect on the overall performance of the model at predicting precipitation rates in the tropics. Given these results we conclude that future studies that look to assess the present day global climate impacts of fire aerosols should consider the need to accurately represent fire episodicity.

Description: Antecedent flow conditions and nitrate concentrations in the Mississippi River Basin Hydrology and Earth System Sciences Discussions, 10, 11451-11484, 2013 Author(s): J. C. Murphy, R. M. Hirsch, and L. A. Sprague The influence of antecedent flow conditions on nitrate concentrations was explored at eight sites in the Mississippi River Basin, USA. Antecedent moisture conditions have been shown to influence nutrient export from small, relatively homogenous basins, but this influence has not been observed at a regional or continental scale. Antecedent flow conditions were quantified as the ratio between the mean daily flow of the previous year and the mean daily flow from the period of record ( Q ratio), and the Q ratio was statistically related to nitrate anomalies (the unexplained variability in nitrate concentration after filtering out season, long-term trend, and contemporaneous flow effects) at each site. Nitrate anomaly and Q ratio were negatively related at three of the four major tributary sites and upstream in the Mississippi River, indicating that when the previous year was drier than average, at these sites, nitrate concentrations were higher than expected. The strength of these relationships increased when data were subdivided by contemporaneous flow conditions. Five of the eight sites had significant negative relationships ( p ≤ 0.05) at high or moderately high contemporaneous flows, suggesting nitrate that accumulates in these basins during a drought is flushed during subsequent storm events. At half of the sites, when flow during the previous year was 50% drier than average, nitrate concentration can be from 9 and 27% higher than nitrate concentrations that follow a year with average daily flow. Conversely, nitrate concentration can be from 8 and 21% lower than expected when the previous year was 50% wetter than average. These relationships between nitrate concentration and Q ratio serve as the basis for future studies that can better define specific hydrologic processes occurring during and after a drought, which influence nitrate concentration, such as the duration or magnitude of low flows, and the timing of low and high flows.

Description: A new data set of soil mineralogy for dust-cycle modeling Atmospheric Chemistry and Physics Discussions, 13, 23943-23993, 2013 Author(s): E. Journet, Y. Balkanski, and S. P. Harrison The mineralogy of airborne dust affects the impact of dust particles on direct and indirect radiative forcing, on atmospheric chemistry and on biogeochemical cycling. It is determined partly by the mineralogy of the dust-source regions and partly by size-dependent fractionation during erosion and transport. Here we present a data set that characterizes the clay and silt sized fractions of global soil units in terms of the abundance of 12 minerals that are important for dust-climate interactions: quartz, feldspars, illite, smectite, kaolinite, chlorite, vermiculite, mica, calcite, gypsum, hematite and goethite. The basic mineralogical information is derived from the literature, and is then expanded following explicit rules, in order to characterize as many soil units as possible. We present three alternative realisations of the mineralogical maps that account for the uncertainties in the mineralogical data. We examine the implications of the new database for calculations of the single scattering albedo of airborne dust and thus for dust radiative forcing.

Description: Contribution of snow and glacier melt to discharge for highly glacierised catchments in Norway Hydrology and Earth System Sciences Discussions, 10, 11485-11517, 2013 Author(s): M. Engelhardt, T. V. Schuler, and L. M. Andreassen Glacierised catchments significantly alter the streamflow regime due to snow and glacier meltwater contribution to discharge. In this study, we modelled the mass balance and discharge rates for three highly glacierised catchments (〉50% glacier cover) in western Norway over the period 1961–2012. The spatial pattern of the catchments follows a gradient in climate continentality from west to east. The model uses gridded temperature and precipitation values from seNorge ( http://senorge.no ) as input which are available at a daily resolution. It accounts for accumulation of snow, transformation of snow to firn and ice, evaporation and melt. The model was calibrated for each catchment based on measurements of seasonal glacier mass-balances and daily discharge rates. For validation, daily melt rates were compared with measurements from sonic rangers located in the ablation zones of two of the glaciers and an uncertainty analysis was performed for the third catchment. The discharge contributions from snowmelt, glacier melt and rain were analysed with respect to spatial variations and temporal evolution. The model simulations reveal an increase of the relative contribution from glacier melt for the three catchments from less than 10% in the early 1990s to 15–30% in the late 2000s. The decline in precipitation by 10–20% in the same period was therefore overcompensated resulting in an increase of the annual discharge by 5–20%. Annual discharge sums and annual glacier melt are strongest correlated with annual and winter precipitation at the most maritime glacier and, with increased climate continentality, variations in both glacier melt contribution and annual discharge are becoming stronger correlated with variations in summer temperatures.

Description: Growth of sulphuric acid nanoparticles under wet and dry conditions Atmospheric Chemistry and Physics Discussions, 13, 24087-24125, 2013 Author(s): L. Škrabalová, D. Brus, T. Anttila, V. Ždímal, and H. Lihavainen New particle formation, which greatly influences the number concentrations and size distributions of an atmospheric aerosol, is often followed by a rapid growth of freshly formed particles. The initial growth of a newly formed aerosol is the crucial process determining the fraction of nucleated particles growing into cloud condensation nuclei sizes, which have a significant influence on climate. In this study, we report the laboratory observations of the growth of nanoparticles produced by nucleation of H 2 SO 4 and water in a laminar flow tube at temperatures of 283, 293 and 303 K, under dry (a relative humidity of 1%) and wet conditions (relative humidity of 30%) and residence times of 30, 45, 60 and 90 s. The initial H 2 SO 4 concentration spans the range from 2 × 10 8 to 1.4 × 10 10 molecule cm −3 and the calculated wall losses of H 2 SO 4 were assumed to be diffusion limited. The detected particle number concentrations, measured by the Ultrafine Condensation Particle Counter (UCPC) and Differential Mobility Particle Sizer (DMPS), were found to depend strongly on the residence time. Hygroscopic particle growth, presented by growth factors, was found to be in good agreement with the previously reported studies. The experimental growth rates ranged from 20 nm h −1 to 890 nm h −1 at RH 1% and from 7 nm h −1 to 980 nm h −1 at RH 30% and were found to increase significantly with the increasing concentration of H 2 SO 4 . Increases in the nucleation temperature had a slight enhancing effect on the growth rates under dry conditions. The influence of relative humidity on growth was not consistent – at lower H 2 SO 4 concentrations, the growth rates were higher under dry conditions while at H 2 SO 4 concentrations greater than 1×10 9 molecule cm −3 the growth rates were higher under wet conditions. The growth rates show only a weak dependence on the residence time. The experimental observations were compared with predictions made using a numerical model, which investigates the growth of particles with three different extents of neutralization by the ammonia NH 3 : (1) pure H 2 SO 4 – H 2 O particles (2) particles formed by ammonium bisulphate, (NH 4 )HSO 4 (3) particles formed by ammonium sulphate, (NH 4 ) 2 SO 4 . The highest growth rates were found for ammonium sulphate particles. Since the model accounting for the initial H 2 SO 4 concentration predicted the experimental growth rates correctly, our results suggest that the commonly presumed diffusional wall losses of H 2 SO 4 are not so significant. We therefore assume that there are not only losses of H 2 SO 4 on the wall but also a flux of H 2 SO 4 molecules from the wall into the flow tube, the effect being more profound under dry conditions and at higher temperatures of the tube wall. Based on a comparison with the atmospheric observations, our results indicate that sulphuric acid alone can not explain the growth rates of particles formed in the atmosphere.

Description: Bias correction can modify climate model-simulated precipitation changes without adverse affect on the ensemble mean Hydrology and Earth System Sciences Discussions, 10, 11585-11611, 2013 Author(s): E. P. Maurer and D. W. Pierce When applied to remove climate model biases in precipitation, quantile mapping can in some settings modify the simulated trends. This has important implications when the precipitation will be used to drive an impacts model that is sensitive to changes in precipitation. We use daily precipitation output from 12 general circulation models (GCMs) over the conterminous United States interpolated to a common 1° grid, and gridded observations aggregated to the same scale, to compare precipitation differences before and after quantile mapping bias correction. The change in seasonal mean (winter, DJF, and summer, JJA) precipitation between different 30-yr historical periods is compared to examine (1) the consensus among GCMs as to whether the bias correction tends to amplify or diminish their simulated precipitation trends, and (2) whether the modification of the change in precipitation tends to improve or degrade the correspondence to observed changes in precipitation for the same periods. In some cases, for a particular GCM, the trend modification can be as large as the original simulated change, though the areas where this occurs varies among GCMs so the ensemble median shows smaller trend modification. In specific locations and seasons the trend modification by quantile mapping improves correspondence with observed trends, and in others it degrades it. In the majority of the domain the ensemble median is for little effect on the correspondence of simulated precipitation trends with observed. This highlights the need to use an ensemble of GCMs rather than relying on a small number of models to estimate impacts.

Description: Impacts of different plant functional types on ambient ozone predictions in the Seoul Metropolitan Areas (SMA), Korea Atmospheric Chemistry and Physics Discussions, 13, 24925-24973, 2013 Author(s): H.-K. Kim, J.-H. Woo, R. S. Park, C. H. Song, J.-H. Kim, S.-J. Ban, and J.-H. Park Plant functional type (PFT) distributions affect the results of biogenic emission modeling as well as O 3 and PM simulations using chemistry-transport models (CTMs). This paper analyzes the variations of both surface biogenic VOC emissions and O 3 concentrations due to changes in the PFT distributions in the Seoul Metropolitan Areas, Korea. Also, this paper attempts to provide important implications for biogenic emissions modeling studies for CTM simulations. MM5-MEGAN-SMOKE-CMAQ model simulations were implemented over the Seoul Metropolitan Areas in Korea to predict surface O 3 concentrations for the period of 1 May to 31 June 2008. Starting from MEGAN biogenic emissions analysis with three different sources of PFT input data, US EPA CMAQ O 3 simulation results were evaluated by surface O 3 monitoring datasets and further considered on the basis of geospatial and statistical analyses. The three PFT datasets considered were "(1)KORPFT", developed with a region specific vegetation database; (2) CDP, adopted from US NCAR; and (3) MODIS, reclassified from the NASA Terra and Aqua combined land cover products. Comparisons of MEGAN biogenic emission results with the three different PFT data showed that broadleaf trees (BT) are the most significant contributor, followed by needleleaf trees (NT), shrub (SB), and herbaceous plants (HB) to the total biogenic volatile organic compounds (BVOCs). In addition, isoprene from BT and terpene from NT were recognized as significant primary and secondary BVOC species in terms of BVOC emissions distributions and O 3 -forming potentials in the study domain. Multiple regression analyses with the different PFT data (δO 3 vs. δPFTs) suggest that KORPFT can provide reasonable information to the framework of MEGAN biogenic emissions modeling and CTM O 3 predictions. Analyses of the CMAQ performance statistics suggest that deviations of BT areas can significantly affect CMAQ isoprene and O 3 predictions. From further evaluations of the isoprene and O 3 prediction results, we explored the PFT area-loss artifact that occurs due to geographical disparity between the PFT and leaf area index distributions, and can cause increased bias in CMAQ O 3 . Thus, the PFT-loss artifact must be a source of limitation in the MEGAN biogenic emission modeling and the CTM O 3 simulation results. Time changes of CMAQ O 3 distributions with the different PFT scenarios suggest that hourly and local impacts from the different PFT distributions on occasional inter-deviations of O 3 are quite noticeable, reaching up to 10 ppb. Exponentially diverging hourly BVOC emissions and O 3 concentrations with increasing ambient temperature suggest that the use of representative PFT distributions becomes more critical for O 3 air quality modeling (or forecasting) in support of air quality decision-making and human health studies.

Description: Incidence of rough and irregular atmospheric ice particles from Small Ice Detector 3 measurements Atmospheric Chemistry and Physics Discussions, 13, 24975-25012, 2013 Author(s): Z. Ulanowski, P. H. Kaye, E. Hirst, R. S. Greenaway, R. J. Cotton, E. Hesse, and C. T. Collier The knowledge of properties of ice crystals such as size, shape, concavity and roughness is critical in the context of radiative properties of ice and mixed phase clouds. Limitations of current cloud probes to measure these properties can be circumvented by acquiring two-dimensional light scattering patterns instead of particle images. Such patterns were obtained in situ for the first time using the Small Ice Detector 3 (SID-3) probe during several flights in a variety of mid-latitude mixed phase and cirrus clouds. The patterns are analyzed using several measures of pattern texture, selected to reveal the magnitude of particle roughness or complexity. The retrieved roughness is compared to values obtained from a range of well-characterized test particles in the laboratory. It is found that typical in situ roughness corresponds to that found in the rougher subset of the test particles, and sometimes even extends beyond the most extreme values found in the laboratory. In this study we do not differentiate between small-scale, fine surface roughness and large-scale crystal complexity. Instead, we argue that both can have similar manifestations in terms of light scattering properties and also similar causes. Overall, the in situ data is consistent with ice particles with highly irregular or rough surfaces being dominant. Similar magnitudes of roughness were found in growth and sublimation zones of cirrus. The roughness was found to be negatively correlated with the halo ratio, but not with other thermodynamic or microphysical properties found in situ. Slightly higher roughness was observed in cirrus forming in clean oceanic airmasses than in a continental, polluted one. Overall, the roughness and complexity is expected to lead to increased shortwave cloud reflectivity, in comparison with cirrus composed of more regular, smooth ice crystal shapes. These findings put into question suggestions that climate could be modified through aerosol seeding to reduce cirrus cover and optical depth, as the seeding may result in decreased shortwave reflectivity.

Description: The effect of training image and secondary data integration with multiple-point geostatistics in groundwater modeling Hydrology and Earth System Sciences Discussions, 10, 11829-11860, 2013 Author(s): X. He, T. O. Sonnenborg, F. Jørgensen, and K. H. Jensen Multiple-point geostatistic simulation (MPS) has recently become popular in stochastic hydrogeology, primarily because of its capability to derive multivariate distributions from the training image (TI). However, its application in three dimensional simulations has been constrained by the difficulty of constructing 3-D TI. The object-based TiGenerator may be a useful tool in this regard; yet the sensitivity of model predictions to the training image has not been documented. Another issue in MPS is the integration of multiple geophysical data. The best way to retrieve and incorporate information from high resolution geophysical data is still under discussion. This work shows that TI from TiGenerator delivers acceptable results when used for groundwater modeling, although the TI directly converted from high resolution geophysical data leads to better simulation. The model results also indicate that soft conditioning in MPS is a convenient and efficient way of integrating secondary data such as 3-D airborne electromagnetic data, but over conditioning has to be avoided.

Description: Multi-decadal river flows variations in France Hydrology and Earth System Sciences Discussions, 10, 11861-11900, 2013 Author(s): J. Boé and F. Habets In this article, multi-decadal variations in French hydroclimate are investigated, with a specific focus on river flows. Based on long observed series, it is shown that river flows in France generally exhibit large multi-decadal variations on the historical period, especially in spring. Differences of means between two 21 yr periods of the 20th century as large as 40% are indeed found for many gauging stations. Multi-decadal spring river flows variations are associated with variations in spring precipitation and temperature. These multi-decadal variations in precipitation are themselves found to be driven by large-scale atmospheric circulation, more precisely by a multi-decadal oscillation in a sea level pressure dipole between western Europe and the East Atlantic. It is suggested that the Atlantic Multidecadal Variability, the main mode of decadal variability in the North Atlantic/Europe sector, controls those variations in large-scale circulation and is therefore the main ultimate driver of multi-decadal variations in spring river flows. Multi-decadal variations in river flows in other seasons, and in particular summer, are also noted. As they are not associated with significant surface climate anomalies (i.e. temperature, precipitation) in summer, other mechanisms are investigated based on hydrological simulations. The impact of climate variations in spring on summer soil moisture, and the impact of soil moisture in summer on the runoff to precipitation ratio, could potentially play a role in multi-decadal summer river flows variations. The large amplitude of the multi-decadal variations in French river flows suggests that internal variability may play a very important role in the evolution of river flows during the next decades, potentially temporarily limiting, reversing or seriously aggravating the long-term impacts of anthropogenic climate change.

Description: Factors controlling pollutant plume length downwind of major roadways in nocturnal surface inversions Atmospheric Chemistry and Physics Discussions, 13, 25253-25290, 2013 Author(s): W. Choi, A. M. Winer, and S. E. Paulson A curve fit method using a Gaussian dispersion model solution was successfully applied to obtain both dispersion coefficients and a particle number emission factor (PNEF) directly from ultrafine particle (UFP) concentration profiles observed downwind of major roadways in California's South Coast Air Basin (SoCAB). The Briggs' formulation for the vertical dispersion parameter σ z was adopted in this study due to its better performance in describing the observed profiles compared to other formulations examined. The two dispersion coefficients in Briggs' formulation, α and β, ranged from 0.02 to 0.07 and from −0.5 × 10 −3 to 2.8 × 10 −3 , respectively, for the four freeway transects studied and are significantly different for freeways passing over vs. under the street on which measurements of the freeway plume were made. These ranges are wider than literature values for α and β under stable conditions. The dispersion coefficients derived from observations showed strong correlations with both surface meteorology (wind speed/direction, temperature, and air stability) and differences in concentrations between the background and plume peak. The relationships were applied to predict freeway plume transport using a multivariate regression, and produced excellent agreement with observed UFP concentration profiles. The mean PNEF for a mixed vehicle fleet on the four freeways was estimated as 1.2 × 10 14 particles mi −1 vehicle −1 , which is about 15% of the value estimated in 2001 for the I-405 freeway, implying significant reductions in UFP emissions over the past decade in the SoCAB.

Description: Summer Sea Ice Albedo in the Arctic in CMIP5 models Atmospheric Chemistry and Physics Discussions, 13, 25219-25251, 2013 Author(s): T. Koenigk, A. Devasthale, and K.-G. Karlsson Spatial and temporal variations of summer sea ice albedo over the Arctic are analyzed using an ensemble of historical CMIP5 model simulations. The results are compared to the CLARA-SAL product that is based on long-term satellite observations. The summer sea ice albedo varies substantially among CMIP5 models and many models show large biases compared to the CLARA-SAL product. Single summer months show an extreme spread of ice albedo among models; July-values vary between 0.3 and 0.7 for individual models. The CMIP5 ensemble mean, however, agrees relatively well in the Central Arctic but shows too high ice albedo near the ice edges and coasts. In most models, the ice albedo is spatially too uniformly distributed. The summer to summer variations seem to be underestimated in many global models and almost no model is able to fully reproduce the temporal evolution of ice albedo throughout the summer. While the satellite observations indicate the lowest ice albedos during August, the models show minimum values in July and substantially higher values in August. Instead, the June values are often lower in the models than in the satellite observations. This is probably due to too high surface temperatures in June, leading to an early start of the melt season and too cold temperatures in August causing an earlier refreezing in the models. The summer sea ice albedo in the CMIP5 models is strongly governed by surface temperature and snow conditions, particularly during the period of melt onset in early summer and refreezing in late summer. The summer surface net solar radiation of the ice covered Arctic areas is highly related to the ice albedo in the CMIP5 models. However, the impact of the ice albedo on the sea ice conditions in the CMIP5 models is not clearly visible. This indicates the importance of other Arctic and large scale processes for the sea ice conditions.

Description: Intercontinental transport and deposition patterns of atmospheric mercury from anthropogenic emissions Atmospheric Chemistry and Physics Discussions, 13, 25185-25218, 2013 Author(s): L. Chen, H.-H. Wang, J.-F. Liu, W. Zhang, D. Hu, C. Chen, and X.-J. Wang Global policies that regulate anthropogenic mercury emissions to the environment require quantitative and comprehensive source–receptor relationships for mercury emissions, transport and deposition among major continental regions. In this study, we use the GEOS-Chem model to establish source–receptor relationships among eleven major continental regions worldwide. Source–receptor relationships for surface mercury concentrations (SMC) show that some regions (e.g. East Asia, the Indian subcontinent and Europe) should be responsible for their local surface Hg(II) and Hg(P) concentrations because of near-field transport and deposition contributions from their local anthropogenic emissions (up to 64% and 71% for Hg(II) and Hg(P), respectively, over East Asia). We define region of primary influence (RPI) and region of secondary influence (RSI) to establish intercontinental influence patterns. Results indicate that East Asia is SMC RPI for almost all other regions, while Europe, Russia and the Indian subcontinent also make some contributions to SMC over some receptor regions because they are dominant RSI source regions. Source–receptor relationships for mercury deposition show that approximately 16% and 17% of dry and wet deposition, respectively, over North America originate from East Asia, indicating that trans-pacific transport of East Asian emissions is the major foreign source of mercury deposition in North America. Europe, Southeast Asia and the Indian subcontinent are also important mercury deposition sources for some receptor regions because they are dominant RSI. We also quantify seasonal variation on mercury deposition contributions over other regions from East Asia. Results show that mercury deposition (including dry and wet) contributions from East Asia over the Northern Hemisphere receptor regions (e.g. North America, Europe, Russia, Middle East and Middle Asia) vary seasonally, with the maximum values in summer and minimum values in winter. The opposite seasonal pattern occurs on mercury dry deposition contributions over Southeast Asia and the Indian subcontinent.

Description: Teleconnection analysis of runoff and soil moisture over the Pearl River basin in South China Hydrology and Earth System Sciences Discussions, 10, 11943-11982, 2013 Author(s): J. Niu, J. Chen, and B. Sivakumar This study explores the teleconnection of two climatic patterns, namely the El Niño-Southern Oscillation (ENSO) and the Indian Ocean Dipole (IOD), with hydrological processes over the Pearl River basin in South China. The Variable Infiltration Capacity (VIC) model is used to simulate the daily hydrological processes over the basin for the study period 1952–2000, and then, using the simulation results, the time series of the monthly runoff and soil moisture anomalies for its ten sub-basins are aggregated. Wavelet analysis is performed to explore the variability properties of these time series at 49 timescales ranging from 2 months to 9 yr. Use of wavelet coherence and rank correlation method reveals that the dominant variabilities of the time series of runoff and soil moisture are basically correlated with IOD. The influences of ENSO on the terrestrial hydrological processes are mainly found in the eastern sub-basins. The teleconnections between climatic patterns and hydrological variability also serve as a reference basis for inferences on the occurrence of extreme hydrological events (e.g. floods and droughts).

Description: Balloon-borne match measurements of mid-latitude cirrus clouds Atmospheric Chemistry and Physics Discussions, 13, 25417-25479, 2013 Author(s): A. Cirisan, B. P. Luo, I. Engel, F. G. Wienhold, U. K. Krieger, U. Weers, G. Romanens, G. Levrat, P. Jeannet, D. Ruffieux, R. Philipona, B. Calpini, P. Spichtinger, and T. Peter Observations of persistent high supersaturations with respect to ice inside cirrus clouds are challenging our understanding of cloud microphysics and of climate feedback processes in the upper troposphere. Single measurements of a cloudy air mass provide only a snapshot from which the persistence of ice supersaturation cannot be judged. We introduce here the "cirrus match technique" to obtain information of the evolution of clouds and their saturation ratio. The aim of these coordinated balloon soundings is to analyze the same air mass twice. To this end the standard radiosonde equipment is complemented by a frost point hygrometer "SnowWhite" and a particle backscatter detector "COBALD" (Compact Optical Backscatter Aerosol Detector). Extensive trajectory calculations based on regional weather model COSMO forecasts are performed for flight planning and COSMO analyses are used as basis for comprehensive microphysical box modeling (with grid scale 2 km and 7 km, respectively). Here we present the results of matching a cirrus cloud to within 2–15 km, realized on 8 June 2010 over Payerne, Switzerland, and a location 120 km downstream close to Zurich. A thick cirrus was detected over both measurement sites. We show that in order to quantitatively reproduce the measured particle backscatter ratios, the small-scale temperature fluctuations not resolved by COSMO must be superimposed on the trajectories. The stochastic nature of the fluctuations is captured by ensemble calculations. Possibilities for further improvements in the agreement with the measured backscatter data are investigated by assuming a very slow mass accommodation of water on ice, the presence of heterogeneous ice nuclei, or a wide span of (spheroidal) particle shapes. However, the resulting improvements from microphysical refinements are moderate and comparable in magnitude with changes caused by assuming different regimes of temperature fluctuations for clear sky or cloudy sky conditions, highlighting the importance of a proper treatment of subscale fluctuations. The model yields good agreement with the measured backscatter over both sites and reproduces the measured saturation ratios with respect to ice over Payerne. Conversely, the 30% in-cloud supersaturation measured in a massive, 4-km thick cloud layer over Zurich cannot be reproduced, irrespective of the choice of meteorological or microphysical model parameters. The measured supersaturation can only be explained by either resorting to an unknown physical process, which prevents the ice particles from consuming the excess humidity, or – much more likely – by a measurement error, such as a contamination of the sensor housing of the SnowWhite hygrometer by a precipitation drop from a mixed phase cloud just below the cirrus layer or from some very slight rain in the boundary layer. This uncertainty calls for in-flight checks or calibrations of hygrometers under the extreme humidity conditions in the upper troposphere.

Description: An explicit study of aerosol mass conversion and its parameterization in warm rain formation of cumulus clouds Atmospheric Chemistry and Physics Discussions, 13, 25481-25536, 2013 Author(s): J. Sun, J. Fen, and R. K. Ungar The life time of atmospheric aerosols is highly affected by in-cloud scavenging processes. Aerosol mass conversion from aerosols embedded in cloud droplets into aerosols embedded in raindrops is a pivotal pathway for wet removal of aerosols in clouds. The aerosol mass conversion rate in the bulk microphysics parameterizations is always assumed to be linearly related to the precipitation production rate, which includes the cloud water autoconversion rate and the cloud water accretion rate. The ratio of the aerosol mass concentration conversion rate to the cloud aerosol mass concentration has typically been considered to be the same as the ratio of the precipitation production rate to the cloud droplet mass concentration. However, the mass of an aerosol embedded in a cloud droplet is not linearly proportional to the mass of the cloud droplet. A simple linear relationship cannot be drawn between the precipitation production rate and the aerosol mass concentration conversion rate. In this paper, we studied the evolution of aerosol mass concentration conversion rates in a warm rain formation process with a 1.5-dimensional non-hydrostatic convective cloud and aerosol interaction model in the bin microphysics. We found that the ratio of the aerosol mass conversion rate to the cloud aerosol mass concentration can be statistically expressed by the ratio of the precipitation production rate to the cloud droplet mass concentration with an exponential function. We further gave some regression equations to determine aerosol conversions in the warm rain formation under different threshold radii of raindrops and different aerosol size distributions.

Description: Hydrological functions of sinkholes and characteristics of point recharge in groundwater basins Hydrology and Earth System Sciences Discussions, 10, 11423-11449, 2013 Author(s): N. Somaratne, K. Smettem, J. Lawson, K. Nguyen, and J. Frizenschaf Karstic limestone aquifers are hydrologically and hydrochemically extremely heterogeneous and point source recharge via sinkholes and fissures is a common feature. We studied three groundwater systems in karstic settings dominated by point source recharge in order to assess the relative contributions to total recharge from point sources using chloride and δ 18 O relations. Preferential groundwater flows were observed through an inter-connected network of highly conductive zones with groundwater mixing along flow paths. Measurements of salinity and chloride indicated that fresh water pockets exist at point recharge locations. A measurable fresh water plume develops only when a large quantity of surface water enters the aquifer as a point recharge source. The difference in chloride concentrations in diffuse and point recharge zones decreases as aquifer saturated thickness increases and the plumes become diluted through mixing. The chloride concentration in point recharge fluxes crossing the watertable plane can remain at or near surface runoff chloride concentrations, rather than in equilibrium with groundwater chloride. In such circumstances the conventional chloride mass balance method that assumes equilibrium of recharge water chloride with groundwater requires modification to include both point and diffuse recharge mechanisms.

Description: Global and regional impacts of HONO on the chemical composition of clouds and aerosols Atmospheric Chemistry and Physics Discussions, 13, 23599-23638, 2013 Author(s): Y. F. Elshorban, P. J. Crutzen, B. Steil, A. Pozzer, H. Tost, and J. Lelieveld Nitrous acid (HONO) photolysis can significantly increase HO x (OH+HO 2 ) radical formation, enhancing organic and inorganic oxidation products in polluted regions, especially during winter. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that HONO can significantly enhance aerosol sulphate (S(VI)), mainly due to the increased formation of H 2 SO 4 . Even though in-cloud aqueous phase oxidation of dissolved SO 2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H 2 O 2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO 3 formation and N 2 O 5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model-measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and the central role of cloud chemical processing in aerosol formation.

Description: Injection heights of springtime biomass burning plumes over the Peninsular Southeast Asia and their impacts on pollutant long-range transport Atmospheric Chemistry and Physics Discussions, 13, 23781-23816, 2013 Author(s): Y. Jian and T.-M. Fu We analyzed observations from the Multi-angle Imaging SpectroRadiometer (MISR) to determine the injection heights of biomass burning smoke plumes over the Peninsular Southeast Asia (PSEA) in spring, with the goal of evaluating the impacts on pollutant long-range transport. We retrieved the heights of twenty-two thousand MISR smoke pixels from 607 smoke plumes over the PSEA during February to April of the years 2001–2010. Forty-five percent of the analyzed smoke pixels were above the local mean boundary layer (1 km) at MISR overpass time (10:30 a.m. local time). We used the GEOS-Chem model to simulate the transport of PSEA biomass burning pollutants in March 2001. We found that the direct injection of 40% of the PSEA biomass burning emissions had little impact on the long-range transport of CO to downwind regions, compared to a control simulation where all biomass burning emissions were released in the boundary layer. This was because CO at the surface over the PSEA was efficiently lifted into the free troposphere by deep convection associated with synoptic-scale weather systems. For pollutants with lifetimes shorter than the synoptic timescale, such as black carbon aerosol (BC), their long-range transport was much more sensitive to the initial plume injection height. The direct injection of NO x from PSEA biomass burning into the free troposphere drove increased formation and transport of PAN, which in turn led to significant increases of ozone over downwind southern China and northwestern Pacific. The Pacific subtropical high transported PSEA biomass burning pollutants to the marine boundary layer over the tropical northwestern Pacific. We compared our model results to aircraft measurements over the northwestern Pacific during the TRACE-P campaign (March 2001). The direct injection of 40% of the PSEA biomass burning pollutants in the free troposphere in the model led to a more pronounced BC peak at 3 km over the northwestern Pacific, which was in better agreement with the aircraft observations compared to the control simulation. Our analyses highlighted the point that the injection heights of smoke plumes pose large uncertainty to the interpretation of BC measurements downwind of biomass burning regions.

Description: Influence of surface morphology on the immersion mode ice nucleation efficiency of hematite particles Atmospheric Chemistry and Physics Discussions, 13, 23757-23780, 2013 Author(s): N. Hiranuma, N. Hoffmann, A. Kiselev, A. Dreyer, K. Zhang, G. Kulkarni, T. Koop, and O. Möhler In this paper, the effect of the morphological modification of aerosol particles with respect to heterogeneous ice nucleation is comprehensively investigated for laboratory-generated hematite particles as a model substrate for atmospheric dust particles. The surface area-scaled ice nucleation efficiencies of monodisperse cubic hematite particles and milled hematite particles were measured with a series of expansion cooling experiments using the Aerosol Interaction and Dynamics in the Atmosphere (AIDA) cloud simulation chamber. Complementary off-line characterization of physico-chemical properties of both hematite subsets were also carried out with scanning electron microscopy (SEM), energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS), and an electro-kinetic particle charge detector to further constrain droplet-freezing measurements of hematite particles. Additionally, an empirical parameterization derived from our laboratory measurements was implemented in the single-column version of the Community Atmospheric Model version 5 (CAM5) to investigate the model sensitivity in simulated ice crystal number concentration on different ice nucleation efficiencies. From an experimental perspective, our results show that the immersion mode ice nucleation efficiency of milled hematite particles is almost an order of magnitude higher at −35.2 °C 〈 T 〈 −33.5 °C than that of the cubic hematite particles, indicating a substantial effect of morphological irregularities on immersion mode freezing. Our modeling results similarly show that the increased droplet-freezing rates of milled hematite particles lead to about one order magnitude higher ice crystal number in the upper troposphere than cubic hematite particles. Overall, our results suggest that the surface irregularities and associated active sites lead to greater ice activation through droplet-freezing.

Description: Study of the unknown HONO daytime source at an European suburban site during the MEGAPOLI summer and winter field campaigns Atmospheric Chemistry and Physics Discussions, 13, 23639-23690, 2013 Author(s): V. Michoud, A. Colomb, A. Borbon, K. Miet, M. Beekmann, M. Camredon, B. Aumont, S. Perrier, P. Zapf, G. Siour, W. Ait-Helal, C. Afif, A. Kukui, M. Furger, J. C. Dupont, M. Haeffelin, and J. F. Doussin Nitrous acid measurements were carried out during the MEGAPOLI summer and winter field campaigns at SIRTA observatory in Paris surroundings. Highly variable HONO levels were observed during the campaigns, ranging from 10 ppt to 500 ppt in summer and from 10 ppt to 1.7 ppb in winter. Significant HONO mixing ratios have also been measured during daytime hours, comprised between some tenth of ppt and 200 ppt for the summer campaign and between few ppt and 1 ppb for the winter campaign. Ancillary measurements, such as NO x , O 3 , photolysis frequencies, meteorological parameters (pressure, temperature, relative humidity, wind speed and wind direction), black carbon concentration, total aerosol surface area, boundary layer height and soil moisture, were conducted during both campaigns. In addition, for the summer period, OH radical measurements were made with a CIMS (Chemical Ionisation Mass Spectrometer). This large dataset has been used to investigate the HONO budget in a suburban environment. To do so, calculations of HONO concentrations using PhotoStationary State (PSS) approach have been performed, for daytime hours. The comparison of these calculations with measured HONO concentrations revealed an underestimation of the calculations making evident a missing source term for both campaigns. This unknown HONO source exhibits a bell shaped like average diurnal profile with a maximum around noon of approximately 0.7 ppb h −1 and 0.25 ppb h −1 , during summer and winter respectively. This source is the main HONO source during daytime hours for both campaigns. In both cases, this source shows a slight positive correlation with J (NO 2 ) and the product between J (NO 2 ) and soil moisture. This original approach had, thus, indicated that this missing source is photolytic and might be heterogeneous occurring on ground surface and involving water content available at the ground.

Description: Relationship between Amazon biomass burning aerosols and rainfall over La Plata Basin Atmospheric Chemistry and Physics Discussions, 13, 23995-24021, 2013 Author(s): G. Camponogara, M. A. F. Silva Dias, and G. G. Carrió High aerosol loads are discharged into the atmosphere by biomass burning in Amazon and Central Brazil during the dry season. These particles can interact with clouds as cloud condensation nuclei (CCN) changing cloud microphysics and radiative properties and, thereby, affecting the radiative budget of the region. Furthermore, the biomass burning aerosols can be transported by the low level jet (LLJ) to La Plata Basin where many mesoscale convective systems (MCS) are observed during spring and summer. This work proposes to investigate whether the aerosols from biomass burning may affect the MCS in terms of rainfall over La Plata Basin during spring. Since the aerosol effect is very difficult to isolate because convective clouds are very sensitive to small environment disturbances, detailed analyses using different techniques are used. The binplot, 2D histograms and combined empirical orthogonal function (EOF) methods are used to separate certain environment conditions with the possible effects of aerosol loading. Reanalysis 2, TRMM-3B42 and AERONET data are used from 1999 up to 2012 during September-December. The results show that there are two patterns associated to rainfall-aerosol interaction in La Plata Basin: one in which the dynamic conditions are more important than aerosols to generate rain; and a second one where the aerosol particles have a role in rain formation, acting mainly to suppress rainfall over La Plata Basin.

Description: Size-resolved aerosol composition and link to hygroscopicity at a forested site in Colorado Atmospheric Chemistry and Physics Discussions, 13, 23817-23843, 2013 Author(s): E. J. T. Levin, A. J. Prenni, B. Palm, D. Day, P. Campuzano-Jost, P. M. Winkler, S. M. Kreidenweis, P. J. DeMott, J. Jimenez, and J. N. Smith Aerosol hygroscopicity describes the ability of a particle to take up water and form a cloud droplet. Modeling studies have shown sensitivity of precipitation-producing cloud systems to the availability of aerosol particles capable of serving as cloud condensation nuclei (CCN), and hygroscopicity is a key parameter controlling the number of available CCN. Continental aerosol is typically assumed to have a representative hygroscopicity parameter, κ, of 0.3; however, in remote locations this value can be lower due to relatively large mass fractions of organic components. To further our understanding of aerosol properties in remote areas, we measured size-resolved aerosol chemical composition and hygroscopicity in a forested, mountainous site in Colorado during the six-week BEACHON-RoMBAS campaign. This campaign followed a year-long measurement period at this site, and results from the intensive campaign shed light on the previously reported seasonal cycle in aerosol hygroscopicity. New particle formation events were observed routinely at this site and nucleation mode composition measurements indicated that the newly formed particles were predominantly organic. These events likely contribute to the dominance of organic species at smaller sizes, where aerosol organic mass fractions of non-refractory components were between 70–90%. Corresponding aerosol hygroscopicity was observed to range from κ = 0.15–0.22, with hygroscopicity increasing with particle size. Aerosol chemical composition measured by an Aerosol Mass Spectrometer and calculated from hygroscopicity measurements agreed very well during the intensive study with an assumed value of κ org = 0.13 resulting in the best agreement.

Description: Atmospheric parameters in a subtropical cloud regime transition derived by AIRS+MODIS – observed statistical variability compared to ERA-Interim Atmospheric Chemistry and Physics Discussions, 13, 24051-24085, 2013 Author(s): M. M. Schreier, B. H. Kahn, K. Sušelj, J. Karlsson, S. C. Ou, Q. Yue, and S. L. Nasiri Cloud occurrence, microphysical and optical properties and atmospheric profiles within a subtropical cloud regime transition in the northeastern Pacific Ocean are obtained from a synergistic combination of the Atmospheric Infrared Sounder (AIRS) and the MODerate resolution Imaging Spectroradiometer (MODIS). The observed cloud parameters and atmospheric thermodynamic profile retrievals are binned by cloud type and analyzed based on their probability density functions (PDFs). Comparison of the PDFs to data from the European Center for Medium Range Weather Forecasting Re-analysis (ERA-Interim) shows a strong difference in the occurrence of the different cloud types compared to clear sky. An increasing non-Gaussian behavior is observed in cloud optical thickness (τ c ), effective radius ( r e ) and cloud top temperature ( T c ) distributions from Stratocumulus to Trade Cumulus, while decreasing values of lower tropospheric stability are seen. However, variations in the mean, width and shape of the distributions are found. The AIRS potential temperature (θ) and water vapor ( q ) profiles in the presence of varying marine boundary layer (MBL) cloud types show overall similarities to the ERA-Interim in the mean profiles, but differences arise in the higher moments at some altitudes. The differences between the PDFs from AIRS+MODIS and ERA-Interim make it possible to pinpoint systematic errors in both systems and helps to understand joint PDFs of cloud properties and coincident thermodynamic profiles from satellite observations.

Description: Climate information based streamflow and rainfall forecasts for Huai River Basin using Hierarchical Bayesian Modeling Hydrology and Earth System Sciences Discussions, 10, 11559-11584, 2013 Author(s): X. Chen, Z. Hao, N. Devineni, and U. Lall A Hierarchal Bayesian model for forecasting regional summer rainfall and streamflow season-ahead using exogenous climate variables for East Central China is presented. The model provides estimates of the posterior forecasted probability distribution for 12 rainfall and 2 streamflow stations considering parameter uncertainty, and cross-site correlation. The model has a multilevel structure with regression coefficients modeled from a common multivariate normal distribution results in partial-pooling of information across multiple stations and better representation of parameter and posterior distribution uncertainty. Covariance structure of the residuals across stations is explicitly modeled. Model performance is tested under leave-10-out cross-validation. Frequentist and Bayesian performance metrics used include Receiver Operating Characteristic, Reduction of Error, Coefficient of Efficiency, Rank Probability Skill Scores, and coverage by posterior credible intervals. The ability of the model to reliably forecast regional summer rainfall and streamflow season-ahead offers potential for developing adaptive water risk management strategies.

Description: Establishing the contribution of lawn mowing to atmospheric aerosol levels in American suburbs Atmospheric Chemistry and Physics Discussions, 13, 24435-24480, 2013 Author(s): R. M. Harvey, J. Zahardis, and G. A. Petrucci Green leaf volatiles (GLVs) are a class of wound-induced volatile organic compounds emitted by several plant species. Turfgrasses emit a complex profile of GLVs upon mowing, as evidenced by the "freshly cut grass" smell, some of which are readily oxidized in the atmosphere to contribute to secondary organic aerosol (SOA). The contribution of lawn mowing-induced SOA production may be especially impactful at the urban/suburban interface, where urban hubs provide a source of anthropogenic oxidants and SOA while suburban neighborhoods have the potential to emit large quantities of reactive, mow-induced GLVs. This interface provides a unique opportunity to study aerosol formation in a multi-component system and at a regionally relevant scale. Freshly cut grass was collected from a study site in Essex Junction, Vermont and was placed inside a 775 L Teflon experimental chamber. Thermal desorption gas chromatography mass spectrometry (TD-GC/MS) was used to characterize the emitted GLV profile. Ozone was introduced to the experimental chamber and TD-GC/MS was used to monitor the consumption of these GLVs and the subsequent evolution of gas phase products while a scanning mobility particle sizer was used to continuously measure aerosol size distributions and mass loadings as a result of grass clipping ozonolysis. Freshly cut grass found to emit a complex mixture of GLVs, dominated by cis -3-hexenyl acetate and cis -3-hexenol, which were released at an initial rate of 1.8 (±0.5) μg and 0.07 (±0.03) μg per square meter of lawn mowed with each mowing. Chamber studies using pure standards of cis -3-hexenyl acetate (CHA) and cis -3-hexenol (HXL) were found to have aerosol yields of 1.2 (±1.1)% and 3.3 (±3.1)%, respectively. Using these aerosol yields and the emission rate of these CHA and HXL by grass, SOA evolution by ozonolysis of grass clippings was predicted. However, the measured SOA mass produced from the ozonolysis of grass clippings exceeded the predicted amount, by upwards of ~ 150%. The ozonolysis of a mixture of CHA and HXL representative of environmental mixing ratios also failed to accurately model the SOA mass produced by grass clippings. Aerial photographs and geospatial analysis were used to determine the turfgrass coverage in a suburban neighborhood, which was then used along with measured SOA production as a function of grass mowed to determine that lawn mowing has the potential to contribute 47 μg m −2 SOA to the atmosphere per mowing event by ozonolysis, which cannot be modeled solely by the ozonolysis of CHA, HXL or a representative mixture of the two.

Description: Global distributions and trends of atmospheric ammonia (NH 3 ) from IASI satellite observations Atmospheric Chemistry and Physics Discussions, 13, 24301-24342, 2013 Author(s): M. Van Damme, L. Clarisse, C. L. Heald, D. Hurtmans, Y. Ngadi, C. Clerbaux, A. J. Dolman, J. W. Erisman, and P. F. Coheur Ammonia (NH 3 ) emissions in the atmosphere have strongly increased in the past decades, largely because of the intensive livestock production and use of fertilizers. As a short-lived species, NH 3 is highly variable in the atmosphere and its concentration is generally small, except in and close to local source areas. While ground-based measurements are possible, they are challenging and sparse. Advanced infrared sounders in orbit have recently demonstrated their capability to measure NH 3 , offering a new tool to refine global and regional budgets. In this paper we describe an improved retrieval scheme of NH 3 total columns from the measurements of the Infrared Atmospheric Sounding Interferometer (IASI). It exploits the hyperspectral character of this instrument by using an extended spectral range (800–1200 cm −1 ) where NH 3 is optically active. This scheme consists of the calculation of a dimensionless spectral index from the IASI level1C radiances, which is subsequently converted to a total NH 3 column using look-up-tables built from forward radiative transfer model simulations. We show how to retrieve the NH 3 total columns from IASI quasi-globally and twice daily, above both land and sea, without large computational resources and with an improved detection limit. The retrieval also provides error characterization on the retrieved columns. Five years of IASI measurements (1 November 2007 to 31 October 2012) have been processed to acquire the first global and multiple-year dataset of NH 3 total columns, which are evaluated and compared to similar products from other retrieval methods. Spatial distributions from the five years dataset are provided and analyzed at global and regional scales. We show in particular the ability of this method to identify smaller emission sources than those reported previously, as well as transport patterns above sea. The five year time series is further examined in terms of seasonality and inter-annual variability (in particular as a function of fire activity) separately for the Northern and Southern Hemispheres.

Description: Aircraft measurements of polar organic tracer compounds in tropospheric particles (PM 10 ) over Central China Atmospheric Chemistry and Physics Discussions, 13, 24481-24516, 2013 Author(s): P. Q. Fu, K. Kawamura, Y. F. Cheng, S. Hatakeyama, A. Takami, H. Li, and W. Wang Atmospheric aerosol samples were collected by aircraft at low to middle altitudes (0.8–3.5 km a.g.l.) over Central East to West China during summer 2003 and spring 2004. The samples were analyzed for polar organic compounds using a technique of solvent extraction/BSTFA derivatization/gas chromatography-mass spectrometry. Biogenic secondary organic aerosol (SOA) tracers from the oxidation of isoprene were found to be more abundant in summer (3.3–138 ng m −3 , mean 39 ng m −3 ) than in spring (3.2–42 ng m −3 , 15 ng m −3 ), while α/β-pinene and β-caryophyllene SOA tracers showed similar abundance between these two seasons. A strong positive correlation ( R 2 =0.83) between levoglucosan and β-caryophyllinic acid was found in the spring samples versus a weak correlation ( R 2 =0.17) in the summer samples, implying substantial contributions from biomass burning to the β-caryophyllinic acid production in spring. Two organic nitrogen species (oxamic acid and carbamide) were detected in the aircraft aerosol samples and their concentrations were comparable to those of biogenic SOA tracers. Most of the POA and SOA tracers were less abundant at higher altitudes, suggesting they are of ground surface origin, either being directly emitted from anthropogenic/natural sources on the ground surface, or rapidly formed through photooxidation of their precursors emitted from the ground surface and then diluted during uplifting into the troposphere. This study demonstrates that primary biological aerosols, biogenic SOA, and organic nitrogen species are important components of organic aerosols in the troposphere over Central China.

Description: Black carbon emissions from in-use ships: a California regional assessment Atmospheric Chemistry and Physics Discussions, 13, 24675-24712, 2013 Author(s): G. M. Buffaloe, D. A. Lack, E. J. Williams, D. Coffman, K. L. Hayden, B. M. Lerner, S-M. Li, I. Nuaaman, P. Massoli, T. B. Onasch, P. K. Quinn, and C. D. Cappa Black carbon (BC) mass emission factors (EF BC ; g-BC (kg-fuel) −1 ) from a variety of ocean going vessels have been determined from measurements of BC and carbon dioxide (CO 2 ) concentrations in ship plumes intercepted by the R/V Atlantis during the 2010 California Nexus (CalNex) campaign. The ships encountered were all operating within 24 nautical miles of the California coast and were utilizing relatively low sulphur fuels. Black carbon concentrations within the plumes, from which EF BC values are determined, were measured using four independent instruments: a photoacoustic spectrometer and a particle soot absorption photometer, which measure light absorption, and a single particle soot photometer and soot particle aerosol mass spectrometer, which measure the mass concentration of refractory BC directly. The measured EF BC have been divided into vessel type categories and engine type categories, from which averages have been determined. The geometric average EF BC , determined from over 71 vessels and 135 plumes encountered, was 0.31 g-BC (kg-fuel) −1 . The most frequent engine type encountered was the slow speed diesel (SSD), and the most frequent SSD vessel type was the cargo ship sub-category. Average and median EF BC values from the SSD category are compared with previous observations from the Texas Air Quality Study (TexAQS) in 2006, during which the ships encountered were predominately operating on high sulphur fuels. There is a statistically significant difference between the EF BC values from CalNex and TexAQS for SSD vessels and for the cargo and tanker ship types within this engine category. The CalNex EF BC values are lower than those from TexAQS, suggesting that operation on lower sulphur fuels is associated with smaller EF BC values.

Description: A case study into the measurement of ship emissions from plume intercepts of the NOAA Ship Miller Freeman Atmospheric Chemistry and Physics Discussions, 13, 24635-24674, 2013 Author(s): C. D. Cappa, E. J. Williams, D. A. Lack, G. M. Buffaloe, D. Coffman, K. L. Hayden, S. C. Herndon, B. M. Lerner, S-M. Li, P. Massoli, R. McLaren, I. Nuaaman, T. B. Onasch, and P. K. Quinn Emissions factors (EFs) for gas and sub-micron particle-phase species were measured in intercepted plumes as a function of vessel speed from an underway research vessel, the NOAA Ship Miller Freeman , operating a medium-speed diesel engine on low-sulfur marine gas oil. For many of the particle-phase species, EFs were determined using multiple measurement methodologies, allowing for an assessment of how well EFs from different techniques agree. The total sub-micron PM (PM 1 ) was dominated by particulate black carbon (BC) and particulate organic matter (POM), with an average POM / BC ratio of 1.3. Consideration of the POM / BC ratios observed here with literature studies suggests that laboratory and in-stack measurement methods may over-estimate primary POM EFs relative to those observed in emitted plumes. Comparison of four different methods for black carbon measurement indicates that careful attention must be paid to instrument limitations and biases when assessing EF BC . Particulate sulfate (SO 4 2− ) EFs were extremely small and the particles emitted by Miller Freeman were inefficient as cloud condensation nuclei (CCN), even at high super saturations, consistent with the use of very low sulfur fuel and the overall small emitted particle sizes. All measurement methodologies consistently demonstrate that the measured EFs (fuel mass basis) for PM 1 mass, BC and POM decreased as the ship slowed. Particle number EFs were approximately constant across the speed change, with a shift towards smaller particles being emitted at slower speeds. Emissions factors for gas-phase CO and formaldehyde (HCHO) both increased as the vessel slowed, while EFs for NO x decreased and SO 2 EFs were approximately constant.

Description: Heterogeneous reaction of N 2 O 5 with illite and Arizona Test Dust particles Atmospheric Chemistry and Physics Discussions, 13, 24855-24884, 2013 Author(s): M. J. Tang, G. Schuster, and J. N. Crowley The heterogeneous reaction of N 2 O 5 with airborne illite and Arizona Test Dust particles was investigated at room temperature and at different relative humidities using an atmospheric pressure aerosol flow tube. N 2 O 5 at concentrations in the range 8 to 24×10 12 molecule cm −3 was monitored using thermal-dissociation cavity ring-down spectroscopy at 662 nm. At zero relative humidity a large uptake coefficient of N 2 O 5 to illite was obtained, γ(N 2 O 5 ) = 0.09, which decreased to 0.04 as relative humidity was increased to 67%. In contrast, the uptake coefficient derived for ATD is much lower (~ 0.006) and, within experimental uncertainty, independent of relative humidity (0–67%). Potential explanations are given for the significant differences between the uptake behaviour for ATD and illite and the results are compared with uptake coefficients for N 2 O 5 on other mineral surfaces.

Description: A case study of sea breeze blocking regulated by sea surface temperature along the English south coast Atmospheric Chemistry and Physics Discussions, 13, 24785-24807, 2013 Author(s): J. K. Sweeney, J. M. Chagnon, and S. L. Gray The sensitivity of sea breeze structure to sea surface temperature (SST) and coastal orography is investigated in convection-permitting Met Office Unified Model simulations of a case study along the south coast of England. Changes in SST of 1 K are shown to significantly modify the structure of the sea breeze. On the day of the case study the sea breeze was partially blocked by coastal orography, particularly within Lyme Bay. The extent to which the flow is blocked depends strongly on the static stability of the marine boundary layer. In experiments with colder SST, the marine boundary layer is more stable, and the degree of blocking is more pronounced. The implications of prescribing fixed SST from climatology in numerical weather prediction model forecasts of the sea breeze are discussed.

Description: Using a WRF simulation to examine regions where convection impacts the Asian summer monsoon anticyclone Atmospheric Chemistry and Physics Discussions, 13, 24809-24853, 2013 Author(s): N. K. Heath and H. E. Fuelberg The Asian summer monsoon is a prominent feature of the global circulation that is associated with an upper-level anticyclone (ULAC) that stands out vividly in satellite observations of trace gases. The ULAC also is an important region of troposphere-to-stratosphere transport. We ran the Weather Research and Forecasting (WRF) model at convective-permitting scales (4 km grid spacing) between 10–20 August 2012 to understand the role of convection in transporting boundary layer air into the upper-level anticyclone. Such high-resolution modeling of the Asian ULAC previously has not been documented in the literature. Comparison of our WRF simulation with reanalysis and satellite observations showed that WRF simulated the atmosphere sufficiently well to be used to study convective transport into the ULAC. A back-trajectory analysis based on hourly WRF output showed that 〉 90% of convectively influenced parcels reaching the ULAC came from the Tibetan Plateau (TP) and the southern slope (SS) of the Himalayas. A distinct diurnal cycle is seen in the convective trajectories, with their greatest impact occurring between 1600–2300 local solar time. This finding highlights the role of "everyday" diurnal convection in transporting boundary layer air into the ULAC. WRF output at 15 min intervals was produced for 16 August to examine the convection in greater detail. This high-temporal output revealed that the weakest convection in the study area occurred over the TP. However, because the TP is at 3000–5000 m a.m.s.l., its convection does not have to be as strong to reach the ULAC as in lower altitude regions. In addition, because the TP's elevated heat source is a major cause of the ULAC, we propose that convection over the TP and the neighboring SS is ideally situated geographically to impact the ULAC. The vertical mass flux of water vapor into the ULAC also was calculated. Results show that the TP and SS regions dominate other Asian regions in transporting moisture vertically into the ULAC. Because convection reaching the ULAC is more widespread over the TP than nearby, we propose that the abundant convection partially explains the TP's dominant water vapor fluxes. In addition, greater outgoing longwave radiation reaches the upper levels of the TP due to its elevated terrain. This creates a warmer ambient upper level environment, allowing parcels with greater saturation mixing ratios to enter the ULAC. Lakes in the Tibetan Plateau are shown to provide favorable conditions for deep convection during the night.

Description: A spatial bootstrap technique for parameter estimation of rainfall annual maxima distribution Hydrology and Earth System Sciences Discussions, 10, 11755-11794, 2013 Author(s): F. Uboldi, A. N. Sulis, C. Lussana, M. Cislaghi, and M. Russo Estimation of extreme event distributions and depth-duration-frequency (DDF) curves is achieved at any target site by repeated sampling among all available raingauge data in the surrounding area. The estimate is computed over a gridded domain in Northern Italy, using precipitation time series from 1929 to 2011, including data from historical analog stations and from the present-day automatic observational network. The presented local regionalisation naturally overcomes traditional station-point methods, with their demand of long historical series and their sensitivity to very rare events occurring at very few stations, possibly causing unrealistic spatial gradients in DDF relations. At the same time, the presented approach allows for spatial dependence, necessary in a geographical domain such as Lombardy, complex for both its topography and its climatology. The bootstrap technique enables evaluating uncertainty maps for all estimated parameters and for rainfall depths at assigned return periods.

Description: Overview of the first HyMeX Special Observation Period over Italy: observations and model results Hydrology and Earth System Sciences Discussions, 10, 11643-11710, 2013 Author(s): R. Ferretti, E. Pichelli, S. Gentile, I. Maiello, D. Cimini, S. Davolio, M. M. Miglietta, G. Panegrossi, L. Baldini, F. Pasi, F. S. Marzano, A. Zinzi, S. Mariani, M. Casaioli, G. Bartolini, N. Loglisci, A. Montani, C. Marsigli, A. Manzato, A. Pucillo, M. E. Ferrario, V. Colaiuda, and R. Rotunno During the first Hymex campaign (5 September–6 November 2012) referred to as Special Observation Period (SOP-1), dedicated to heavy precipitation events and flash floods in Western Mediterranean, three Italian hydro-meteorological monitoring sites were activated: Liguria-Tuscany, North-Eastern Italy and Central Italy. The extraordinary deployment of advanced instrumentation, including instrumented aircrafts, and the use of several different operational weather forecast models has allowed an unprecedented monitoring and analysis of high impact weather events around the Italian hydro-meteorological sites. This activity has seen the strict collaboration between the Italian scientific and operational communities. In this paper, an overview of the Italian organization during the SOP-1 is provided, and selected Intensive Observation Periods (IOPs) are described. A significant event for each Italian target area is chosen for this analysis: IOP2 (12–13 September 2012) in North-Eastern Italy, IOP13 (15–16 October 2012) in Central Italy and IOP19 (3–5 November 2012) in Liguria and Tuscany. For each IOP the meteorological characteristics, together with special observations and weather forecasts, are analyzed with the aim of highlighting strengths and weaknesses of the forecast modeling systems. Moreover, using one of the three events, the usefulness of different operational chains is highlighted.

Description: Correcting basin-scale snowfall in a mountainous basin using a distributed snowmelt model and remote sensing data Hydrology and Earth System Sciences Discussions, 10, 11711-11753, 2013 Author(s): M. Shrestha, L. Wang, T. Koike, H. Tsutsui, Y. Xue, and Y. Hirabayashi Adequate estimation of the spatial distribution of snowfall is critical in hydrologic modeling. However, this is a well-known problem in estimating basin-scale snowfall, especially in mountainous basins with data scarcity. This study focuses on correction and estimation of this spatial distribution, which considers topographic effects within the basin. A method is proposed that optimizes an altitude-based snowfall correction factor ( C fsnow ). This is done through multi-objective calibration of a spatially distributed, multilayer energy and water balance-based snowmelt model (WEB-DHM-S) with observed discharge and remotely sensed snow cover data from the Moderate Resolution Imaging Spectroradiometer (MODIS). The Shuffled Complex Evolution – University of Arizona automatic search algorithm is used to obtain the optimal value of C fsnow for minimum cumulative error in discharge and snow cover simulations. Discharge error is quantified by Nash–Sutcliffe efficiency and relative volume deviation, and snow cover error was estimated by pixel-by-pixel analysis. The study region is the heavily snow-fed Yagisawa Basin of the Upper Tone River in northeast Japan. First, the system was applied to one snow season (2002–2003), obtaining an optimized C fsnow of 0.0007 m −1 . For validation purposes, the optimized C fsnow was implemented to correct snowfall in 2004, 2002 and 2001. Overall, the system was effective, implying improvements in correlation of simulated vs. observed discharge and snow cover. The 4 yr mean of basin-average snowfall for the corrected spatial snowfall distribution was 1160 mm (780 mm before correction). Execution of sensitivity runs against other model input and parameters indicated that C fsnow could be affected by uncertainty in shortwave radiation and setting of the threshold air temperature parameter. Our approach is suitable to correct snowfall and estimate its distribution in poorly-gauged basins, where elevation dependence of snowfall amount is strong.

Description: Attribution of hydrologic forecast uncertainty within scalable forecast windows Hydrology and Earth System Sciences Discussions, 10, 11795-11828, 2013 Author(s): L. Yang, F. Tian, Y. Sun, X. Yuan, and H. Hu Hindcasts based on the Extended Streamflow Prediction (ESP) approach are carried out in a typical rainfall-dominated basin in China, aiming to examine the roles of initial condition (IC), future atmospheric forcing (FC) and hydrologic model uncertainty (MU) in the streamflow forecast skill. The combined effects of IC and FC are explored within the framework of a forecast window. By implementing virtual numerical simulations without the consideration of MU, it is found that the dominance of IC could last up to 90 days in dry season, while its impact gives way to FC for lead times exceeding 30 days in the wet season. The combined effects of IC and FC on the forecast skill are further investigated by proposing a dimensionless parameter ( β ) that represents the ratio of the total amount of initial water storage and the incoming rainfall. The forecast skill increases exponentially with β , and varies greatly in different forecast windows. Moreover, the influence of MU on forecast skill is examined by focusing on the uncertainty of model parameters. Two different hydrologic model calibration strategies are carried out. The results indicate that the uncertainty of model parameters exhibits a more significant influence on the forecast skill in the dry season than in the wet season. The ESP approach is more skillful in monthly streamflow forecast during the transition period from wet to dry than otherwise. For the transition period from dry to wet, the low skill of the forecasts could be attributed to the combined effects of IC and FC, but less to the biases in the hydrologic model parameters. For the forecasting in dry season, the usefulness of the ESP approach is heavily dependent on the strategy of the model calibration.

Description: An assessment of the performance of the Monitor for AeRosols and GAses in ambient air (MARGA): a semi-continuous method for soluble compounds Atmospheric Chemistry and Physics Discussions, 13, 25067-25124, 2013 Author(s): I. C. Rumsey, K. A. Cowen, J. T. Walker, T. J. Kelly, E. A. Hanft, K. Mishoe, C. Rogers, R. Proost, G. M. Beachley, G. Lear, T. Frelink, and R. P. Otjes Ambient air monitoring as part of the US Environmental Protection Agency's (US EPA's) Clean Air Status and Trends Network (CASTNet) currently uses filter packs to measure weekly integrated concentrations. The US EPA is interested in supplementing CASTNet with semi-continuous monitoring systems at select sites to characterize atmospheric chemistry and deposition of nitrogen and sulfur compounds at higher time resolution than the filter pack. The Monitor for AeRosols and GAses in ambient air (MARGA) measures water-soluble gases and aerosols at hourly temporal resolution. The performance of the MARGA was assessed under the US EPA Environmental Technology Verification (ETV) program. The assessment was conducted in Research Triangle Park, North Carolina from 8 September–8 October 2010 and focused on gaseous SO 2 , HNO 3 and NH 3 and aerosol SO 4 − , NO 3 − and NH 4 + . Precision of the MARGA was evaluated by calculating the median absolute relative percent difference (MARPD) between paired hourly results from duplicate MARGA units (MUs), with a performance goal of

Description: A conceptual model of check dam hydraulics for gully control Hydrology and Earth System Sciences Discussions, 10, 11901-11941, 2013 Author(s): C. Castillo, R. Pérez, and J. A. Gómez There is little information in scientific literature regarding the modifications induced by check dam systems in flow regimes in restored gully reaches, despite it being a crucial issue for the design of conservation measures. Here, we develop a conceptual model to classify flow regimes in straight rectangular channels for initial and dam-filling conditions as well as a method of estimating efficiency in order to provide guidelines for optimal design. The model integrates several previous mathematical approaches for assessing the main processes involved (hydraulic jump HJ, impact flow, gradually varied flows). Its performance was compared with the simulations obtained from IBER, a bi-dimensional hydrodynamic model. The impact of check dam spacing (defined by the geometric factor of influence c ) on efficiency was explored. Eleven main classifications of flow regimes were identified depending on the element and level of influence. The model produced similar results when compared with IBER, but led to higher estimations of HJ and impact lengths. Total influence guaranteed maximum efficiency and HJ control defining the location of the optimal c . Geometric total influence ( c = 1) was a valid criterion for the different stages of the structures in a wide range of situations provided that hydraulic roughness conditions remained high within the gully, e.g. through revegetation. Our total influence criterion involved shorter spacing than that habitually recommended in technical manuals for restoration, but was in line with those values found in spontaneous and stable step-pools systems, which might serve as a reference for man-made interventions.

Description: Senstitivity of water balance components to environmental changes in a mountainous watershed: uncertainty assessment based on models comparison Hydrology and Earth System Sciences Discussions, 10, 11983-12026, 2013 Author(s): E. Morán-Tejeda, J. Zabalza, K. Rahman, A. Gago-Silva, J. I. López-Moreno, S. Vicente-Serrano, A. Lehmann, C. L. Tague, and M. Beniston This paper evaluates the response of stream flow and other components of the water balance to changes in climate and land-use in a Pyrenean watershed. It further provides a measure of uncertainty in water resources forecasts by comparing the performance of two hydrological models: Soil and Water Assessment Tool (SWAT) and Regional Hydro-Ecological Simulation System (RHESSys). Regional Climate Model outputs for the 2021–2050 time-frame, and hypothetical (but plausible) land-use scenarios considering re-vegetation and wildfire processes were used as inputs to the models. Results indicate an overall decrease in river flows when the scenarios are considered, except for the post-fire vegetation scenario, in which stream flows are simulated to increase. However the magnitude of these projections varies between the two models used, as SWAT tends to produce larger hydrological changes under climate change scenarios, and RHESSys shows more sensitivity to changes in land-cover. The final prediction will therefore depend largely on the combination of the land-use and climate scenarios, and on the model utilized.

Description: Sensitivity of simulated climate to latitudinal distribution of solar insolation reduction in SRM geoengineering methods Atmospheric Chemistry and Physics Discussions, 13, 25387-25415, 2013 Author(s): A. Modak and G. Bala Solar radiation management (SRM) geoengineering has been proposed as a potential option to counteract climate change. We perform a set of idealized geoengineering simulations to understand the global hydrological implications of varying the latitudinal distribution of solar insolation reduction in SRM methods. We find that for a fixed total mass of sulfate aerosols (12.6 Mt of SO 4 ), relative to a uniform distribution which mitigates changes in global mean temperature, global mean radiative forcing is larger when aerosol concentration is maximum at the poles leading to a warmer global mean climate and consequently an intensified hydrological cycle. Opposite changes are simulated when aerosol concentration is maximized in the tropics. We obtain a range of 1 K in global mean temperature and 3% in precipitation changes by varying the distribution pattern: this range is about 50% of the climate change from a doubling of CO 2 . Hence, our study demonstrates that a range of global mean climate states, determined by the global mean radiative forcing, are possible for a fixed total amount of aerosols but with differing latitudinal distribution, highlighting the need for a careful evaluation of SRM proposals.

Description: Source apportionment of PM 10 in a North-Western Europe regional urban background site (Lens, France) using Positive Matrix Factorization and including primary biogenic emissions Atmospheric Chemistry and Physics Discussions, 13, 25325-25385, 2013 Author(s): A. Waked, O. Favez, L. Y. Alleman, C. Piot, J.-E. Petit, T. Delaunay, E. Verlinden, B. Golly, J.-L. Besombes, J.-L. Jaffrezo, and E. Leoz-Garziandia In this work, the source of ambient particulate matter (PM 10 ) collected over a one year period at an urban background site in Lens (France) were determined and investigated using a~Positive Matrix Factorization receptor model (US EPA PMF v3.0). In addition, a Potential Source Contribution Function (PSCF) was performed by means of the Hysplit v4.9 model to assess prevailing geographical origins of the identified sources. A selective iteration process was followed for the qualification of the more robust and meaningful PMF solution. Components measured and used in the PMF include inorganic and organic species: soluble ionic species, trace elements, elemental carbon (EC), sugars alcohols, sugar anhydride, and organic carbon (OC). The mean PM 10 concentration measured from March 2011 to March 2012 was about 21 μg m −3 with typically OM, nitrate and sulfate contributing to most of the mass and accounting respectively for 5.8, 4.5 and 2.3 μg m −3 on a yearly basis. Accordingly, PMF outputs showed that the main emission sources were (in a decreasing order of contribution): secondary inorganic aerosols (28% of the total PM 10 mass), aged marine emissions (19%), with probably predominant contribution of shipping activities, biomass burning (13%), mineral dust (13%), primary biogenic emissions (9%), fresh sea salts (8%), primary traffic emissions (6%) and heavy oil combustion (4%). Significant temporal variations were observed for most of the identified sources. In particular, biomass burning emissions were negligible in summer but responsible for about 25% of total PM 10 and 50% of total OC at wintertime. Conversely, primary biogenic emissions were found to be negligible in winter but to represent about 20% of total PM 10 and 40% of total OC in summer. The latter result calls for more investigations of primary biogenic aerosols using source apportionment studies, which quite usually disregards this type of sources. This study furthermore underlines the major influence of secondary processes during daily threshold exceedances. Finally, apparent discrepancies that could be generally observed between filter-based studies (such as the present one) and Aerosol Mass Spectrometer-based PMF analyses (organic fractions) are also discussed here.

Description: Wind extraction potential from 4D-Var assimilation of O 3 , N 2 O, and H 2 O using a global shallow water model Atmospheric Chemistry and Physics Discussions, 13, 25291-25323, 2013 Author(s): D. R. Allen, K. W. Hoppel, and D. D. Kuhl The wind extraction due to assimilation of trace gas (tracer) data is examined using a 4D-Var data assimilation system based on the shallow water equations coupled to the tracer continuity equation. The procedure is outlined as follows. First, a Nature Run is created, simulating middle stratospheric winter conditions. Second, ozone (O 3 ), nitrous oxide (N 2 O), and water vapor (H 2 O) (treated in this study as passive tracers) are initialized using Microwave Limb Sounder (MLS) mixing ratios at 850 K potential temperature and advected by the Nature Run winds. Third, the initial dynamical conditions are perturbed by using a 6 h offset. Fourth, observations based on the simulated tracer data are then assimilated with a 4D-Var system in which the tracer and winds are coupled via the adjoint of the tracer continuity equation. Finally, the wind extraction potential (WEP) is calculated as the reduction of the Root Mean Square (RMS) vector wind error due to tracer assimilation relative to the total possible reduction from the initial perturbed conditions. For a single 6 h assimilation cycle of "perfect" tracer (unbiased and no imposed random errors), WEP values are 70% for O 3 , 49% for N 2 O and 16% for H 2 O. O 3 and N 2 O provide more wind information than H 2 O due to stronger background gradients relative to the tracer precisions. 10 day multi-cycle simulations with "perfect" tracer result in WEP of 98% for O 3 , 97% for N 2 O, and 90% for H 2 O. There is therefore sufficient information in these fields to nearly completely specify the dynamics, even without assimilation of dynamical information. For assimilation of tracer observations with realistic random noise (based on MLS precision at 10 hPa), the WEP after 10 days decreases to 57% for O 3 , 42% for N 2 O, and 28% for H 2 O. The root-mean-square (RMS) wind errors level out at ~ 1–2 m s −1 for these runs, suggesting a limit to which realistic tracers could constrain the winds, given complete global coverage. With higher observation noise levels, the WEP values decrease further, with negative WEP occurring in cases of very large errors for H 2 O, indicating that assimilation of very noisy observations may worsen the wind fields.

Description: Hydrologic impact of climate change on Murray Hotham catchment of Western Australia: a projection of rainfall-runoff for future water resources planning Hydrology and Earth System Sciences Discussions, 10, 12027-12076, 2013 Author(s): S. A. Islam, M. A. Bari, and A. H. M. F. Anwar Reduction of rainfall and runoff in recent years across South West Western Australia (SWWA) has drawn attention about climate change impact on water resources and its availability in this region. In this paper, hydrologic impact of climate change on Murray Hotham catchment in SWWA is investigated using multi-model ensemble approach. The Land Use Change Incorporated Catchment (LUCICAT) model was used for hydrologic modelling. Model calibration was performed using (5 km) grid rainfall data from Australian Water Availability Project (AWAP). Downscaled and bias corrected rainfall data from 11 General Circulation Models (GCMs) for Intergovernmental Panel on Climate Change (IPCC) emission scenarios A2 and B1 was used in LUCICAT model to derive rainfall and runoff scenarios for 2046–2065 (mid this century) and 2081–2100 (late this century). The results of climate scenarios were compared with observed past (1961–1980) climate. The mean annual rainfall averaged over the catchment during recent time (1981–2000) was reduced by 2.3% with respect to observed past (1961–1980) and resulting runoff reduction was found 14%. Compared to the past, the mean annual rainfall reductions, averaged over 11 ensembles and over the period for the catchment for A2 scenario are 13.6 and 23.6% for mid and late this century respectively while the corresponding runoff reductions are 36 and 74%. For B1 scenario, the rainfall reductions were 11.9 and 11.6% for mid and late this century and corresponding runoff reductions were 31 and 38%. Spatial distribution of rainfall and runoff changes showed that the rate of changes were higher in high rainfall part compared to the low rainfall part. Temporal distribution of rainfall and runoff indicate that high rainfall in the catchment reduced significantly and further reductions are projected resulting significant runoff reductions. A catchment scenario map has been developed through plotting decadal runoff reduction against corresponding rainfall reduction at four gauging stations for observed and projected period. This could be useful for planning future water resources in the catchment. Projection of rainfall and runoff made based on the GCMs varied significantly for the time periods and emission scenarios. Hence, considerable uncertainty involved in this study though ensemble mean was used to explain the findings.

Description: The simulations of sulfuric acid concentration and new particle formation in an urban atmosphere in China Atmospheric Chemistry and Physics Discussions, 13, 14977-15005, 2013 Author(s): Z. B. Wang, M. Hu, D. Mogensen, D. L. Yue, J. Zheng, R. Y. Zhang, Y. Liu, B. Yuan, X. Li, M. Shao, L. Zhou, Z. J. Wu, A. Wiedensohler, and M. Boy Simulations of sulfuric acid concentration and new particle formation are performed by using the zero-dimensional version of the model MALTE (Model to predict new Aerosol formation in the Lower TropospherE) and measurements from the Campaign of Air Quality Research in Beijing and Surrounding areas (CAREBeijing) in 2008. Chemical reactions from the Master Chemical Mechanism Version 3.2 (MCM v3.2) are used in the model. High correlation (slope = 0.72, R = 0.74) between the modelled and observed sulfuric acid concentrations is found during daytime (06:00–18:00). The aerosol dynamics are simulated by the University of Helsinki Multicomponent Aerosol (UHMA) model including several nucleation mechanisms. The results indicate that the model is able to predict the on- and offset of new particle formation in an urban atmosphere in China. In addition, the number concentrations of newly formed particles in kinetic-type nucleation including homogenous homomolecular ( J=K [H 2 SO 4 ] 2 ) and homogenous heteromolecular nucleation involving organic vapours ( J=K het [H 2 SO 4 ][Org]) are in satisfactory agreement with the observations. However, the specific organic compounds possibly participate in the nucleation process should be investigated in further studies.

Description: Upscaling of evapotranspiration fluxes from instantaneous to daytime scales for thermal remote sensing applications Hydrology and Earth System Sciences Discussions, 10, 7325-7350, 2013 Author(s): C. Cammalleri, M. C. Anderson, and W. P. Kustas Four upscaling methods for estimating daytime evapotranspiration (ET) from single time-of-day snapshots, as commonly retrieved using remote sensing, were compared. These methods are based on the assumption of self-preservation of the ratio between ET and a given reference variable over the daytime hours. The analysis was performed using eddy covariance data collected at 12 AmeriFlux towers, sampling a fairly wide range in climatic and land cover conditions. The choice of energy budget closure method significantly impacted performance using different scaling methodologies. Therefore, a statistical evaluation approach was adopted to better account for the inherent uncertainty in ET fluxes using eddy covariance technique. Overall, this approach suggests that at-surface solar radiation is the most robust reference variable amongst those tested, due to high accuracy of upscaled fluxes and absence of systematic biases. Top-of-atmosphere irradiance was also tested and proved to be reliable under near clear-sky conditions, but tended to overestimate the observed daytime ET during cloudy days. Use of reference ET as a scaling flux did not perform as well as the solar radiation method, but similarly had errors with little seasonal dependency. Finally, the commonly-used evaporative fraction method yielded satisfactory results only in summer months, July and August, and tended to underestimate the observations in the fall/winter seasons from November to January at the flux sites studied.

Description: Reductions in aircraft particulate emissions due to the use of Fischer–Tropsch fuels Atmospheric Chemistry and Physics Discussions, 13, 15105-15139, 2013 Author(s): A. J. Beyersdorf, M. T. Timko, L. D. Ziemba, D. Bulzan, E. Corporan, S. C. Herndon, R. Howard, R. Miake-Lye, K. L. Thornhill, E. Winstead, C. Wey, Z. Yu, and B. E. Anderson The use of alternative fuels for aviation is likely to increase due to concerns over fuel security, price stability and the sustainability of fuel sources. Concurrent reductions in particulate emissions from these alternative fuels are expected because of changes in fuel composition including reduced sulfur and aromatic content. The NASA Alternative Aviation Fuel Experiment (AAFEX) was conducted in January–February 2009 to investigate the effects of synthetic fuels on gas-phase and particulate emissions. Standard petroleum JP-8 fuel, pure synthetic fuels produced from natural gas and coal feedstocks using the Fischer–Tropsch (FT) process, and 50% blends of both fuels were tested in the CFM-56 engines on a DC-8 aircraft. To examine plume chemistry and particle evolution with time, samples were drawn from inlet probes positioned 1, 30, and 145 m downstream of the aircraft engines. No significant alteration to engine performance was measured when burning the alternative fuels. However, leaks in the aircraft fuel system were detected when operated with the pure FT fuels as a result of the absence of aromatic compounds in the fuel. Dramatic reductions in soot emissions were measured for both the pure FT fuels (reductions of 84% averaged over all powers) and blended fuels (64%) relative to the JP-8 baseline with the largest reductions at idle conditions. The alternative fuels also produced smaller soot (e.g. at 85% power, volume mean diameters were reduced from 78 nm for JP-8 to 51 nm for the FT fuel), which may reduce their ability to act as cloud condensation nuclei (CCN). The reductions in particulate emissions are expected for all alternative fuels with similar reductions in fuel sulfur and aromatic content regardless of the feedstock. As the plume cools downwind of the engine, nucleation-mode aerosols form. For the pure FT fuels, reductions (94% averaged over all powers) in downwind particle number emissions were similar to those measured at the exhaust plane (84%). However, the blended fuels had less of a reduction (reductions of 30–44%) than initially measured (64%). The likely explanation is that the reduced soot emissions in the blended fuel exhaust plume results in promotion of new particle formation microphysics, rather than coating on pre-existing soot particles, which is dominant in the JP-8 exhaust plume. Downwind particle volume emissions were reduced for both the pure (79 and 86% reductions) and blended FT fuels (36 and 46%) due to the large reductions in soot emissions. In addition, the alternative fuels had reduced particulate sulfate production (near-zero for FT fuels) due to decreased fuel sulfur content. To study the formation of volatile aerosols (defined as any aerosol formed as the plume ages) in more detail, tests were performed at varying ambient temperatures (−4 to 20 °C). At idle, particle number and volume emissions were reduced linearly with increasing ambient temperature, with best fit slopes corresponding to −1.2 × 10 6 # (kg fuel) −1 °C −1 for particle number emissions and −9.7 mm 3 (kg fuel) −1 °C −1 for particle volume emissions. The temperature dependence of aerosol formation can have large effects on local air quality surrounding airports in cold regions. Aircraft produced aerosols in these regions will be much larger than levels expected based solely on measurements made directly at the engine exit plane. The majority (90% at idle) of the volatile aerosol mass formed as nucleation-mode aerosols with a smaller fraction as a soot coating. Conversion efficiencies of up to 3.8% were measured for the partitioning of gas-phase precursors (unburned hydrocarbons and SO 2 ) to form volatile aerosols. Highest conversion efficiencies were measured at 45% power.

Description: Global isoscapes for δ 18 O and δ 2 H in precipitation: improved prediction using regionalized climatic regression models Hydrology and Earth System Sciences Discussions, 10, 7351-7393, 2013 Author(s): S. Terzer, L. I. Wassenaar, L. J. Araguás-Araguás, and P. K. Aggarwal A Regionalized Climatic Water Isotope Prediction (RCWIP) approach, based on the Global Network for Isotopes in Precipitation (GNIP), was demonstrated for the purposes of predicting point- and large-scale spatiotemporal patterns of the stable isotope compositions of water (δ 2 H, δ 18 O) in precipitation around the world. Unlike earlier global domain and fixed regressor models, RCWIP pre-defined thirty-six climatic cluster domains, and tested all model combinations from an array of climatic and spatial regressor variables to obtain the best predictive approach to each cluster domain, as indicated by RMSE and variogram analysis. Fuzzy membership fractions were thereafter used as the weights to seamlessly amalgamate results of the optimized climatic zone prediction models into a single predictive mapping product, such as global or regional amount-weighted mean annual, mean monthly or growing-season δ 18 O/δ 2 H in precipitation. Comparative tests revealed the RCWIP approach outperformed classical global-fixed regression-interpolation based models more than 67% of the time, and significantly improved upon predictive accuracy and precision. All RCWIP isotope mapping products are available as gridded GeoTIFF files from the IAEA website ( www.iaea.org/water ) and are for use in hydrology, climatology, food authenticity, ecology, and forensics.

Description: Undisturbed and disturbed above canopy ponderosa pine emissions: PTR-TOF-MS measurements and MEGAN 2.1 model results Atmospheric Chemistry and Physics Discussions, 13, 15333-15375, 2013 Author(s): L. Kaser, T. Karl, A. Guenther, M. Graus, R. Schnitzhofer, A. Turnipseed, L. Fischer, P. Harley, M. Madronich, D. Gochis, F. N. Keutsch, and A. Hansel We present the first eddy covariance flux measurements of volatile organic compounds (VOCs) using a proton-transfer-reaction time-of-flight mass-spectrometer (PTR-TOF-MS) above a ponderosa pine forest in Colorado, USA. The high mass resolution of the PTR-TOF-MS enabled the identification of chemical sum formulas. During a 30 day measurement period in August and September 2010, 649 different ion mass peaks were detected in the ambient air mass spectrum (including primary ions and mass calibration compounds). Eddy covariance with the vertical wind speed was calculated for all ion mass peaks. On a typical day, 17 ion mass peaks including protonated parent compounds, their fragments and isotopes as well as VOC-H + -water clusters showed a significant flux with daytime average emissions above a reliable flux threshold of 0.1 mg compound m −2 h −1 . These ion mass peaks could be assigned to seven compound classes. The main flux contributions during daytime (10:00–18:00 LT) are attributed to the sum of 2-methyl-3-buten-2-ol (MBO) and isoprene (50%), methanol (12%), the sum of acetic acid and glycolaldehyde (10%) and the sum of monoterpenes (10%). The total MBO + isoprene flux was composed of 10% isoprene and 90% MBO. There was good agreement between the light and temperature dependency of the sum of MBO and isoprene observed for this work and those of earlier studies. The above canopy flux measurements of the sum of MBO and isoprene and the sum of monoterpenes were compared to emissions calculated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN 2.1). The best agreement between MEGAN 2.1 and measurements was reached using emission factors determined from site specific leaf cuvette measurements. While the modelled and measured MBO + isoprene fluxes agree well the emissions of the sum of monoterpenes is underestimated by MEGAN 2.1. This is expected as some factors impacting monoterpene emissions, such as physical damage of needles and branches due to storms, are not included in MEGAN 2.1. After a severe hailstorm event, 22 ion mass peaks (attributed to six compound classes plus some unknown compounds) showed an elevated flux for the two following days. The sum of monoterpene emissions was 4–23 times higher compared to emissions prior to the hailstorm while MBO emissions remained unchanged. If one heavy storm occurs at this site every month we calculate that the monthly monoterpene emissions (in mg compound m −2 ) would be underestimated by 40% if this disturbance source is not considered.

Description: Aerosol variability and atmospheric transport in the Himalayan region from CALIOP 2007–2010 observations Atmospheric Chemistry and Physics Discussions, 13, 15271-15299, 2013 Author(s): S. Bucci, C. Cagnazzo, F. Cairo, L. Di Liberto, and F. Fierli Himalayan Plateau is surrounded by regions with high natural and anthropogenic aerosol emissions that have a strong impact on regional climate. This is particularly critical for the Himalayan glaciers whose equilibrium is also largely influenced by radiative direct and indirect effects induced by aerosol burden. This work focuses on the spatial and vertical distribution of different aerosol types, their seasonal variability and sources. The analysis of the 2007–2010 yr of CALIPSO vertically resolved satellite data allows the identification of spatial patterns of desert dust and carbonaceous particles in different atmospheric layers. Clusters of Lagrangian back-trajectories highlight the transport pathways from source regions during the dusty spring season. The analysis shows a prevalence of dust; at low heights they are distributed mainly north (with a main contribution from the Gobi and Taklamakan deserts) and west of the Tibetan Plateau (originating from the deserts of South-West Asia and advected by the westerlies). Above the Himalayas the dust amount is minor but still not negligible (detectable in around 20% of the measurements), and transport from more distant deserts (Sahara and Arabian Peninsula) is important. Smoke aerosol, produced mainly in North India and East China, is subject to shorter range transport and is indeed observed closer to the sources while there is a limited amount reaching the top of the plateau. Data analysis reveals a clear seasonal variability in the frequencies of occurrence for the main aerosol types; dust is regulated principally by the monsoon dynamics, with maxima of occurrence in spring. The study also highlights relevant interannual differences, showing a larger presence of aerosol in the region during 2007 and 2008 yr.

Description: Quantifying aerosol mixing state with entropy and diversity measures Atmospheric Chemistry and Physics Discussions, 13, 15615-15662, 2013 Author(s): N. Riemer and M. West This paper presents the first quantitative metric for aerosol population mixing state, defined as the distribution of per-particle chemical species composition. This new metric, the mixing state index χ, is an affine ratio of the average per-particle species diversity D α and the bulk population species diversity D γ , both of which are based on information-theoretic entropy measures. The mixing state index χ enables the first rigorous definition of the spectrum of mixing states from so-called external mixture to internal mixture, which is significant for aerosol climate impacts, including aerosol optical properties and cloud condensation nuclei activity. We illustrate the usefulness of this new mixing state framework with model results from the stochastic particle-resolved model PartMC-MOSAIC. These results demonstrate how the mixing state metrics evolve with time for several archetypal cases, each of which isolates a specific process such as coagulation, emission, or condensation. Further, we present an analysis of the mixing state evolution for a complex urban plume case, for which these processes occur simultaneously. We additionally derive theoretical properties of the mixing state index and present a family of generalized mixing state indexes that vary in the importance assigned to low-mass-fraction species.

Description: Water displacement by sewer infrastructure in the Grote Nete catchment, Belgium, and its hydrological regime effects Hydrology and Earth System Sciences Discussions, 10, 7425-7467, 2013 Author(s): D. Vrebos, T. Vansteenkiste, J. Staes, P. Willems, and P. Meire Urbanization and especially impervious areas, in combination with wastewater treatment infrastructure, can exert several pressures on the hydrological cycle. These pressures were studied for the Grote Nete catchment in Belgium (8.18% impervious area and 3.89% effective impervious area), based on a combination of empirical and model-based approaches. The effective impervious area, combined with the extent of the wastewater collection regions which do not coincide with the natural catchment boundaries, was used as an indicator for the urbanization pressure. Our study revealed changes in the total upstream areas of the subcatchments between −16% and +3%, and in upstream impervious areas between −99% and +64%. These changes lead to important inter-catchment water transfers. Based on simulations with a physically-based and spatially-distributed hydrological catchment model, profound impacts of effective impervious area on infiltration and runoff were found. The model results show that the changes in impervious areas and related water displacements in and between catchments due to the installation of the wastewater treatment infrastructure severely impacted low flows, peak flows and seasonal trends. They moreover show that it is difficult, but of utmost importance, to incorporate these pressures and artificial processes in an accurate way during the development of hydrological models for urbanized catchments.

Description: Long-term observations of positive cluster ion concentration, sources and sinks at the high altitude site of the Puy de Dôme Atmospheric Chemistry and Physics Discussions, 13, 14927-14975, 2013 Author(s): C. Rose, J. Boulon, M. Hervo, H. Holmgren, E. Asmi, M. Ramonet, P. Laj, and K. Sellegri Cluster particles (0.8–1.9 nm) are key entities involved in nucleation and new particle formation processes in the atmosphere. Cluster ions were characterized in clear sky conditions at the Puy de Dôme station (1465 m a.s.l). The studied dataset spread over five years (February 2007–February 2012), which provided a unique chance to catch seasonal variations of cluster ion properties at high altitude. Statistical values of the cluster ion concentration and diameter are reported for both positive and negative polarities. Cluster ions were found to be ubiquitous at the Puy de Dôme and displayed an annual variation with lower concentrations in spring. Positive cluster ions were less numerous than negative ones but were larger in diameters. Negative cluster ion properties seemed insensitive to the occurrence of a new particle formation (NPF) event while positive cluster ions appeared to be significantly more numerous and larger on event days. The parameters of the balance equation for the positive cluster concentration are reported, separately for the different seasons and for the NPF event days and non-event days. The steady state assumption suggests that the ionization rate is balanced with two sinks which are the ion recombination and the attachment on aerosol particles, referred as "aerosol ion sink". The aerosol ion sink was found to be higher during the warm season and dominated the loss of ions. The positive ionization rates derived from the balance equation were well correlated with the ionization rates obtained from radon measurement, and they were on average higher in summer and fall compared to winter and spring. Neither the aerosol ion sink nor the ionization rate were found to be significantly different on event days compared to non-event days, and thus they were not able to explain the different positive cluster concentrations between event and non-event days. Hence, the excess of positive small ions on event days may derive from an additional source of ions coupled with the fact that the steady state was not verified on event days.

Description: Review and uncertainty assessment of size-resolved scavenging coefficient formulations for snow scavenging of atmospheric aerosols Atmospheric Chemistry and Physics Discussions, 13, 14823-14869, 2013 Author(s): L. Zhang, X. Wang, M. D. Moran, and J. Feng Theoretical parameterizations for the size-resolved scavenging coefficient for atmospheric aerosol particles scavenged by snow (Λ snow ) need assumptions regarding (i) snow particle–aerosol particle collection efficiency E , (ii) snow particle size distribution N ( D p ), (iii) snow particle terminal velocity V D , and (iv) snow particle cross-sectional area A . Existing formulas for these parameters are reviewed in the present study and uncertainties in Λ snow caused by various combinations of these parameters are assessed. Different formulations of E can cause uncertainties in Λ snow of more than one order of magnitude for all aerosol sizes for typical snowfall intensities. E is the largest source of uncertainty among all the input parameters, similar to rain scavenging of atmospheric aerosols (Λ rain ) as was found in a previous study by Wang et al. (2010). However, other parameters can also cause significant uncertainties in Λ snow , and the uncertainties from these parameters are much larger than for Λ rain . Specifically, different N ( D p ) formulations can cause one-order-of-magnitude uncertainties in Λ snow for all aerosol sizes, as is also the case for a combination of uncertainties from both V D and A . In comparison, uncertainties in Λ rain from N ( D p ) are smaller than a factor of 5 and those from V D are smaller than a factor of 2. Λ snow estimated from one empirical formula generated from field measurements falls in the upper range of, or is slightly higher than, theoretically estimated values. The predicted aerosol concentrations obtained using different Λ snow formulas can differ by a factor of two for just a one-centimeter snowfall (liquid water equivalent of approximately 1 mm). It is likely that, for typical rain and snow event the removal of atmospheric aerosol particles by snow is more effective than removal by rain for equivalent precipitation amounts, although a firm conclusion requires much more evidence.

Description: Atmospheric waves as scaling, turbulent phenomena Atmospheric Chemistry and Physics Discussions, 13, 14797-14822, 2013 Author(s): J. Pinel and S. Lovejoy It is paradoxical that while atmospheric dynamics are highly nonlinear and turbulent that atmospheric waves are commonly modelled by linear or weakly nonlinear theories. We postulate that the laws governing atmospheric waves are on the contrary high Reynold's number ( Re ), emergent laws so that – in common with the emergent high Re turbulent laws – they are also constrained by scaling symmetries. We propose an effective turbulence – wave propagator which corresponds to a fractional and anisotropic extension of the classical wave equation propagator with dispersion relations similar to those of inertial gravity waves (and Kelvin waves) yet with an anomalous (fractional) order H wav /2. Using geostationary IR radiances, we estimate the parameters finding that H wav /2 ≈ 0.17 ± 0.04 (the classical value = 2).

Description: Optimizing Saharan dust CALIPSO retrievals Atmospheric Chemistry and Physics Discussions, 13, 14749-14795, 2013 Author(s): V. Amiridis, U. Wandinger, E. Marinou, E. Giannakaki, A. Tsekeri, S. Basart, S. Kazadzis, A. Gkikas, M. Taylor, J. Baldasano, and A. Ansmann We demonstrate improvements in CALIPSO dust extinction retrievals over North Africa and Europe when corrections are applied regarding the Saharan dust lidar ratio assumption, the separation of dust portion in detected dust mixtures, and the averaging scheme introduced in the Level 3 CALIPSO product. First, a universal, spatially constant lidar ratio of 58 sr instead of 40 sr is applied to individual Level 2 dust-related backscatter products. The resulting aerosol optical depths show an improvement compared with synchronous and co-located AERONET measurements. An absolute bias of the order of −0.03 has been found, improving on the statistically significant biases of the order of −0.10 reported in the literature for the original CALIPSO product. When compared with the MODIS co-located AOD product, the CALIPSO negative bias is even less for the lidar ratio of 58 sr. After introducing the new lidar ratio for the domain studied, we examine potential improvements to the climatological CALIPSO Level 3 extinction product: (1) by introducing a new methodology for the calculation of pure dust extinction from dust mixtures and (2) by applying an averaging scheme that includes zero extinction values for the non-dust aerosol types detected. The scheme is applied at a horizontal spatial resolution of 1° × 1° for ease of comparison with the instantaneous and co-located dust extinction profiles simulated by the BSC-DREAM8b dust model. Comparisons show that the extinction profiles retrieved with the proposed methodology reproduce the well-known model biases per sub-region examined. The very good agreement of the proposed CALIPSO extinction product with respect to AERONET, MODIS and the BSC-DREAM8b dust model, makes this dataset an ideal candidate for the provision of an accurate and robust multi-year dust climatology over North Africa and Europe.

Description: Climatology of pure Tropospheric profiles and column contents of ozone and carbon monoxide using MOZAIC in the mid-northern latitudes (24° N to 50° N) from 1994 to 2009 Atmospheric Chemistry and Physics Discussions, 13, 14695-14747, 2013 Author(s): R. M. Zbinden, V. Thouret, P. Ricaud, F. Carminati, J.-P. Cammas, and P. Nédélec The objective of this paper is to deliver the most accurate ozone (O 3 ) and carbon monoxide (CO) climatology for the pure troposphere only, i.e. exclusively from the ground to the dynamical tropopause on an individual profile basis. The results (profiles and columns) are derived solely from the M easurements of OZ one and water vapour by in-service AI rbus air C raft programme (MOZAIC) over fifteen years (1994–2009). The study, focused on the northern mid-latitudes [24° N–50° N] and [120° W–140° E], includes more than 40 000 profiles over 11 sites to give a quasi-global zonal picture. Considering all the sites, the pure tropospheric column peak-to-peak seasonal cycle ranges are 23.7–43.2 DU for O 3 and 1.7–6.9 × 10 18 mol cm −2 for CO. The maxima of the seasonal cycles are not in phase, occurring in February–April for CO and May–July for O 3 . The phase shift is related to the photochemistry and OH removal efficiencies. The purely tropospheric seasonal profiles are characterized by a typical autumn-winter/spring-summer O 3 dichotomy, (except in Los Angeles, Eastmed – a cluster of Cairo and Tel Aviv – and the regions impacted by the summer monsoon) and a summer-autumn/winter-spring CO dichotomy. We revisit the boundary-layer, mid-tropospheric (MT) and upper-tropospheric (UT) partial columns, using a new monthly-varying MT ceiling. Interestingly, the seasonal cycle maximum of the UT partial columns is shifted from summer to spring for O 3 and to very early spring for CO. Conversely, the MT maximum is shifted from spring to summer and is associated with a summer (winter) MT thickening (thinning). Lastly, the pure tropospheric seasonal cycles derived from our analysis are consistent with the cycles derived from spaceborne measurements, the correlation coefficients being r = 0.6–0.9 for O 3 , and r 〉 0.9 for CO. The cycles observed from space are nevertheless greater than MOZAIC for O 3 (by 9–18 DU) and smaller for CO (up to 1 × 10 18 mol cm −2 ). The larger winter O 3 difference between the two data sets suggests probable stratospheric contamination in satellite data due to the tropopause position. The study underlines the importance of rigorously discriminating between the stratospheric and tropospheric reservoirs and avoiding use of a monthly-averaged tropopause position without this strict discrimination, in order to assess the pure O 3 and CO tropospheric trends.

Description: A climatology of formation conditions for aerodynamic contrails Atmospheric Chemistry and Physics Discussions, 13, 14667-14693, 2013 Author(s): K. Gierens and F. Dilger Aerodynamic contrails are defined in this paper as line shaped ice clouds caused by aerodynamically triggered cooling over the wings of an aircraft in cruise which become visible immediately at the trailing edge of the wing or close to it. Effects at low altitudes like condensation to liquid droplets and their potential heterogeneous freezing are excluded from our definition. We study atmospheric conditions that allow formation of aerodynamic contrails. These conditions are stated and then applied to atmospheric data, first to a special case where an aerodynamic contrail was actually observed and then to a full year of global reanalysis data. We show where, when (seasonal variation), and how frequently (probability) aerodynamic contrails can form, and how this relates to actual patterns of air traffic. We study the formation of persistent aerodynamic contrails as well. Finally we check whether aerodynamic and exhaust contrails can coexist in the atmosphere. We show that visible aerodynamic contrails are possible only in an altitude range between roughly 540 and 250 hPa, and that the ambient temperature is the most important parameter, not the relative humidity. Finally we give an argument for our believe that currently aerodynamic contrails have a much smaller climate effect than exhaust contrails, which may however change in future with more air traffic in the tropics.

Description: Expansion of global drylands under a warming climate Atmospheric Chemistry and Physics Discussions, 13, 14637-14665, 2013 Author(s): S. Feng and Q. Fu Global drylands encompassing hyper-arid, arid, semiarid, and dry subhumid areas cover about 41% of the earth's terrestrial surface and are home to more than a third of the world's population. By analyzing observations for 1948–2008 and climate model simulations for 1948–2100, we show that global drylands have expanded in last sixty years and will continue to expand in the 21st century. By the end of this century, the world's drylands under a high greenhouse gas emission scenario are projected to be 5.8 × 10 6 km 2 (or 10%) larger than in the 1961–1990 climatology. The major expansion of arid regions will occur over southwest North America, the northern fringe of Africa, southern Africa, and Australia, while major expansions of semiarid regions will occur over the north side of the Mediterranean, southern Africa, and North and South America. The global dryland expansions will increase the population affected by water scarcity and land degradations.

Description: The role of horizontal model resolution in assessing the transport of CO in a middle latitude cyclone using WRF-Chem Atmospheric Chemistry and Physics Discussions, 13, 14871-14925, 2013 Author(s): C. A. Klich and H. E. Fuelberg We use the Weather Research and Forecasting with Chemistry (WRF-Chem) online chemical transport model to simulate a middle latitude cyclone in East Asia at three different horizontal resolutions (45, 15, and 5 km grid spacing). The cyclone contains a typical warm conveyor belt (WCB) with an embedded squall line that passes through an area having large surface concentrations (〉400 ppbv) of carbon monoxide (CO). Model output from WRF-Chem is used to compare differences between the large-scale CO vertical transport by the WCB (the 45 km simulation) with the smaller-scale transport due to its convection (the 5 km simulation). Forward trajectories are calculated from WRF-Chem output using HYSPLIT. At 45 km grid spacing, the WCB exhibits gradual ascent, lofting surface CO to 6–7 km. Upon reaching the warm front, the WCB and associated CO ascend more rapidly and later turn eastward over the Pacific Ocean. Convective transport at 5 km resolution with explicitly resolved convection occurs much more rapidly, with surface CO lofted to altitudes greater than 10 km in 1 h or less. We also compute CO vertical mass fluxes to compare differences in transport due to the different grid spacings. Upward CO flux exceeds 110 000 t h −1 in the domain with explicit convection when the squall line is at peak intensity, while fluxes from the two coarser resolutions are an order of magnitude smaller. Specific areas of interest within the 5 km domain are defined to compare the magnitude of convective transport to that within the entire 5 km region. Although convection encompasses only a small portion of the 5 km domain, it is responsible for ~40% of the upward CO transport. We also examine the vertical transport due to a short wave trough and its associated area of convection, not related to the cyclone, that lofts CO to the upper troposphere. Results indicate that fine-scale resolution with explicitly resolved convection is important when assessing the vertical transport of surface emissions in areas of deep convection.

Description: Virtual water trade and development in Africa Hydrology and Earth System Sciences Discussions, 10, 7291-7324, 2013 Author(s): M. Konar and K. Caylor A debate has long existed on the relationships between human population, natural resources, and development. Recent research has expanded this debate to include the impacts of trade; specifically, virtual water trade, or the water footprint of traded commodities. We conduct an empirical analysis of the relationships between virtual water trade, population, and development in Africa. We find that increases in virtual water imports do not lead to increases in population growth nor do they diminish human welfare. We establish a new index of virtual water trade openness and show that levels of undernourishment tend to fall with increased values of virtual water trade openness. Countries with small dam storage capacity obtain a higher fraction of their agricultural water requirements from external sources, which may indicate implicit "infrastructure sharing" across nations. Globally, increased crop exports tends to correlate with increased crop water use efficiency, though this relationship does not hold for Africa. However, internal African trade is much more efficient in terms of embodied water resources than any other region in the world. Thus, internal African trade patterns may be compensating for poor internal production systems.

Description: A Lagrangian view of ozone production tendency in North American outflow in summers 2009 and 2010 Atmospheric Chemistry and Physics Discussions, 13, 15141-15190, 2013 Author(s): B. Zhang, R. C. Owen, J. A. Perlinger, A. Kumar, S. Wu, M. Val Martin, L. Kramer, D. Helmig, and R. E. Honrath The Pico Mountain Observatory, located at 2225 m a.s.l. in the Azores Islands, was established in 2001 to observe long-range transport from North America to the central North Atlantic. In previous research conducted at the Observatory, ozone enhancement (〉55 ppbv) in North American outflows was observed, and efficient ozone production in these outflows was postulated. This study is focused on determining the causes for high d [O 3 ]/ d [CO] values (~1 ppbv ppbv −1 ) observed in summers of 2009 and 2010. The folded retroplume technique, developed by Owen and Honrath (2009), was applied to combine upwind FLEXPART transport pathways with GEOS-Chem chemical fields. This folded result provides a semi-Lagrangian view of polluted North American outflow in terms of physical properties and chemical processes, including production/loss rate of ozone and NO x produced by lightning and thermal decomposition of PAN. Two transport events from North America were identified for detailed analysis. High d [O 3 ]/ d [CO] was observed in both events, but due to differing transport mechanisms, ozone production tendency differed between the two. A layer of net ozone production was found at 2 km a.s.l. over the Azores in the first event plume, apparently driven by PAN decomposition during subsidence of air mass in the Azores-Bermuda High. In the second event, net ozone loss occurred during transport in the lower free troposphere, yet observed d [O 3 ]/ d [CO] was high. We estimate that in both events, CO loss through oxidation contributed significantly to d [O 3 ]/ d [CO] enhancement. Thus, CO is not appropriately used as a passive tracer of pollution in these events. In general, use of d [O 3 ]/ d [CO] as an indicator of net ozone production/loss may be invalid for any situation in which oxidants are elevated. Based on our analysis, use of d [O 3 ]/ d [CO] to diagnose ozone enhancement without verifying the assumption of negligible CO loss is not advisable.

Description: Free troposphere ozone and carbon monoxide over the North Atlantic for 2001–2011 Atmospheric Chemistry and Physics Discussions, 13, 15377-15407, 2013 Author(s): A. Kumar, S. Wu, M. F. Weise, R. Honrath, R. C. Owen, D. Helmig, L. Kramer, M. Val Martin, and Q. Li In-situ measurements of carbon monoxide (CO) and ozone (O 3 ) at the Pico Mountain Observatory (PMO) located in the Azores, Portugal are analyzed together with results from atmospheric chemical transport modeling (GEOS-Chem) and satellite remote sensing (AIRS for CO and TES for O 3 ) to examine the evolution of free-troposphere CO and O 3 over the North Atlantic for 2001–2011. GEOS-Chem captured the seasonal cycles for CO and O 3 well but significantly underestimated the mixing ratios of CO, particularly in spring. Statistically significant (using a significance level of 0.05) decreasing trends were found for both CO and O 3 based on harmonic regression analysis of the measurement data. The best estimates of the trend for CO and O 3 measurements are −0.31 ± 0.30 (2-σ) ppbv yr −1 and −0.21 ± 0.11 (2-σ) ppbv yr −1 , respectively. Similar decreasing trends for both species were obtained with GEOS-Chem simulation results. The major factor contributing to the reported decrease in CO and O 3 mixing ratios at PMO over the past decade is the decline in anthropogenic CO and O 3 -precursor emissions in regions such as North America and Europe. The increase in Asian emissions does not seem to outweigh the impact of these declines resulting in overall decreasing trends for both CO and O 3 . For O 3 , however, increase in atmospheric water vapor content associated with climate change also appears to be a contributing factor causing enhanced destruction of the O 3 during transport from source regions. These hypotheses are supported by results from the GEOS-Chem tagged CO and tagged O 3 simulations.

Description: Mesoscale modeling of smoke transport over the Southeast Asian Maritime Continent: coupling of smoke direct radiative feedbacks below and above the low-level clouds Atmospheric Chemistry and Physics Discussions, 13, 15443-15492, 2013 Author(s): C. Ge, J. Wang, and J. S. Reid The online-coupled Weather Research and Forecasting model with Chemistry (WRF-Chem) is used to simulate the direct and semi-direct radiative impacts of smoke particles over the Southeast Asian Marine Continents (MC, 10° S–10° N, 90° E–150° E) during October 2006 when a significant El Nino event caused the highest biomass burning activity since 1997. With the use of OC (Organic Carbon)/BC (Black Carbon) ratio of 10 in the smoke emission inventory, the baseline simulation shows that the low-level clouds amplifying effect on smoke absorption led to a warming effect at the top-of-atmosphere (TOA) with a domain/monthly average forcing value of ~20 W m −2 over the islands of Borneo and Sumatra. The smoke-induced monthly average daytime heating (0.3 K) that is largely confined above the low-level clouds results in the local convergence over the smoke source region. This heating-induced convergence coupled with daytime planetary boundary layer turbulent mixing, transports more smoke particles above the planetary boundary layer height (PBLH), hence rendering a positive feedback. This positive feedback contrasts with the decrease of cloud fraction resulted from the combined effects of smoke heating within the cloud layer and the more stability in the boundary layer; the latter can be considered as a negative feedback in which decrease of cloud fraction weakens the heating by smoke particles above the clouds. During nighttime, the elevated smoke layer (above clouds in daytime) is decoupled from boundary layer, and the reduction of PBLH due to the residual surface cooling from the daytime lead to the accumulation of smoke particles near the surface. Because of smoke radiative extinction, on monthly basis, the amount of the solar input at the surface is reduced as large as 60 W m −2 , which lead to the decrease of sensible heat, latent heat, 2 m air temperature, and PBLH by a maximum of 20 W m −2 , 20 W m −2 , 1 K, 120 m, respectively. The decrease of boundary layer mixing and the generation of convergence above the PBL also results in a reduction of precipitable water 1–2 km above the PBLH and more precipitable water near the surface and in upper part of the middle troposphere with changes around 0.1 mm. Overall, there is less of a change of column water vapor over the land, and an increase of water vapor amount over the Karimata Strait. The cloud changes over continents are mostly occurred over the islands of Sumatra and Borneo during the daytime, where the low-level cloud fraction decreases more than 10%. However, the change of local wind (include sea breeze) induced by the smoke radiative feedback leads to more convergence over Karimata Strait and south coastal area of Kalimantan during both daytime and night time; consequently, cloud fraction is increased there up to 20%. The sensitivities with different OC/BC ratio show the importance of the smoke single scattering albedo for the smoke semi-direct effects. A case study on 31 October 2006 further demonstrated a much larger (more than twice of the monthly average) feedback induced by smoke aerosols. The decreased sea breeze during big events can lead to prominent increase (40%) of low-level cloud over coastal water. Lastly, the direct and semi-direct radiative impact of smoke particles over the Southeast Asian Marine Continents is summarized as a conceptual model.

Description: Global carbon monoxide products from combined AIRS, TES and MLS measurements on A-train satellites Atmospheric Chemistry and Physics Discussions, 13, 15409-15441, 2013 Author(s): J. X. Warner, R. Yang, Z. Wei, F. Carminati, A. Tangborn, Z. Sun, W. Lahoz, J.-L. Attié, L. El Amraoui, and B. Duncan This study tests a novel methodology to add value to satellite datasets. This methodology, data fusion, is similar to data assimilation, except that the background model-based field is replaced by a satellite dataset, in this case AIRS (Atmospheric Infrared Sounder) carbon monoxide (CO) measurements. The observational information comes from CO measurements with lower spatial coverage than AIRS, namely, from TES (Tropospheric Emission Spectrometer) and MLS (Microwave Limb Sounder). We show that combining these datasets with data fusion uses the higher spectral resolution of TES to extend AIRS CO observational sensitivity to the lower troposphere, a region especially important for air quality studies. We also show that combined CO measurements from AIRS and MLS provide enhanced information in the UTLS (upper troposphere/lower stratosphere) region compared to each product individually. The combined AIRS/TES and AIRS/MLS CO products are validated against DACOM (differential absorption mid-IR diode laser spectrometer) in situ CO measurements from the INTEX-B (Intercontinental Chemical Transport Experiment: MILAGRO and Pacific phases) field campaign and in situ data from HIPPO (HIAPER Pole-to-Pole Observations) flights. The data fusion results show improved sensitivities in the lower and upper troposphere (20–30% and above 20%, respectively) as compared with AIRS-only retrievals, and improved coverage compared with TES and MLS CO data.

Description: An inverse modeling method to assess the source term of the Fukushima nuclear power plant accident using gamma dose rate observations Atmospheric Chemistry and Physics Discussions, 13, 15567-15614, 2013 Author(s): O. Saunier, A. Mathieu, D. Didier, M. Tombette, D. Quélo, V. Winiarek, and M. Bocquet The Chernobyl nuclear accident and more recently the Fukushima accident highlighted that the largest source of error on consequences assessment is the source term including the time evolution of the release rate and its distribution between radioisotopes. Inverse modeling methods, which combine environmental measurements and atmospheric dispersion models, have proven efficient in assessing source term due to an accidental situation (Gudiksen, 1989; Krysta and Bocquet, 2007; Stohl et al., 2012a; Winiarek et al., 2012). Most existing approaches are designed to use air sampling measurements (Winiarek et al., 2012) and some of them also use deposition measurements (Stohl et al., 2012a; Winiarek et al., 2013) but none of them uses dose rate measurements. However, it is the most widespread measurement system, and in the event of a nuclear accident, these data constitute the main source of measurements of the plume and radioactive fallout during releases. This paper proposes a method to use dose rate measurements as part of an inverse modeling approach to assess source terms. The method is proven efficient and reliable when applied to the accident at the Fukushima Daiichi nuclear power plant (FD-NPP). The emissions for the eight main isotopes 133 Xe, 134 Cs, 136 Cs, 137 Cs, 137m Ba, 131 I, 132 I and 132 Te have been assessed. Accordingly, 103 PBq of 131 I, 35.5 PBq of 132 I, 15.5 PBq of 137 Cs and 12 100 PBq of noble gases were released. The events at FD-NPP (such as venting, explosions, etc.) known to have caused atmospheric releases are well identified in the retrieved source term. The estimated source term is validated by comparing simulations of atmospheric dispersion and deposition with environmental observations. The result is that the model-measurement agreement for all of the monitoring locations is correct for 80% of simulated dose rates that are within a factor of 2 of the observed values. Changes in dose rates over time have been overall properly reconstructed, especially in the most contaminated areas to the northwest and south of the FD-NPP. A comparison with observed atmospheric activity concentration and surface deposition shows that the emissions of caesiums and 131 I are realistic but that 132 I and 132 Te are probably underestimated and noble gases are likely overestimated. Finally, an important outcome of this study is that the method proved to be perfectly suited to emergency management and could contribute to improve emergency response in the event of a nuclear accident.

Description: An interdisciplinary swat ecohydrological model to define catchment-scale hydrologic partitioning Hydrology and Earth System Sciences Discussions, 10, 7235-7290, 2013 Author(s): C. L. Shope, G. R. Maharjan, J. Tenhunen, B. Seo, K. Kim, J. Riley, S. Arnhold, T. Koellner, Y. S. Ok, S. Peiffer, B. Kim, J.-H. Park, and B. Huwe Land use and climate change have long been implicated in modifying ecosystem services, such as water quality and water yield, biodiversity, and agricultural production. To account for future effects on ecosystem services, the integration of physical, biological, economic, and social data over several scales must be implemented to assess the effects on natural resource availability and use. Our objective is to assess the capability of the SWAT model to capture short-duration monsoonal rainfall-runoff processes in complex mountainous terrain under rapid, event-driven processes in a monsoonal environment. To accomplish this, we developed a unique quality-control gap-filling algorithm for interpolation of high frequency meteorological data. We used a novel multi-location, multi-optimization calibration technique to improve estimations of catchment-wide hydrologic partitioning. We calibrated the interdisciplinary model to a combination of statistical, hydrologic, and plant growth metrics. In addition, we used multiple locations of different drainage area, aspect, elevation, and geologic substrata distributed throughout the catchment. Results indicate scale-dependent sensitivity of hydrologic partitioning and substantial influence of engineered features. While our model accurately reproduced observed discharge variability, the addition of hydrologic and plant growth objective functions identified the importance of culverts in catchment-wide flow distribution. The results of this study provide a valuable resource to describe landscape controls and their implication on discharge, sediment transport, and nutrient loading. This study also shows the challenges of applying the SWAT model to complex terrain and extreme environments. By incorporating anthropogenic features into modeling scenarios, we can greatly enhance our understanding of the hydroecological impacts on ecosystem services.

Description: Forcing of stratospheric chemistry and dynamics during the Dalton Minimum Atmospheric Chemistry and Physics Discussions, 13, 15061-15104, 2013 Author(s): J. G. Anet, S. Muthers, E. Rozanov, C. C. Raible, T. Peter, A. Stenke, A. I. Shapiro, J. Beer, F. Steinhilber, S. Brönnimann, F. Arfeuille, Y. Brugnara, and W. Schmutz The response of atmospheric chemistry and climate to volcanic eruptions and a decrease in solar activity during the Dalton Minimum is investigated with the fully coupled atmosphere-ocean-chemistry general circulation model SOCOL-MPIOM covering the time period 1780 to 1840 AD. We carried out several sensitivity ensemble experiments to separate the effects of (i) reduced solar ultra-violet (UV) irradiance, (ii) reduced solar visible and near infrared irradiance, (iii) enhanced galactic cosmic ray intensity as well as less intensive solar energetic proton events and auroral electron precipitation, and (iv) volcanic aerosols. The introduced changes of UV irradiance and volcanic aerosols significantly influence stratospheric climate in the early 19th century, whereas changes in the visible part of the spectrum and energetic particles have smaller effects. A reduction of UV irradiance by 15% causes global ozone decrease below the stratopause reaching 8% in the midlatitudes at 5 hPa and a significant stratospheric cooling of up to 2 °C in the midstratosphere and to 6 °C in the lower mesosphere. Changes in energetic particle precipitation lead only to minor changes in the yearly averaged temperature fields in the stratosphere. Volcanic aerosols heat the tropical lower stratosphere allowing more water vapor to enter the tropical stratosphere, which, via HO x reactions, decreases upper stratospheric and mesospheric ozone by roughly 4%. Conversely, heterogeneous chemistry on aerosols reduces stratospheric NO x leading to a 12% ozone increase in the tropics, whereas a decrease in ozone of up to 5% is found over Antarctica in boreal winter. The linear superposition of the different contributions is not equivalent to the response obtained in a simulation when all forcing factors are applied during the DM – this effect is especially well visible for NO x /NO y . Thus, this study highlights the non-linear behavior of the coupled chemistry-climate system. Finally, we conclude that especially UV and volcanic eruptions dominate the changes in the ozone, temperature and dynamics while the NO x field is dominated by the EPP. Visible radiation changes have only very minor effects on both stratospheric dynamics and chemistry.

Description: Estimation of aerosol water and chemical composition from AERONET at Cabauw, the Netherlands Atmospheric Chemistry and Physics Discussions, 13, 15191-15232, 2013 Author(s): A. J. van Beelen, G. J. H. Roelofs, O. P. Hasekamp, J. S. Henzing, and T. Röckmann Remote sensing of aerosols provides important information on the atmospheric aerosol abundance. However, due to the hygroscopic nature of aerosol particles observed aerosol optical properties are influenced by atmospheric humidity, and the measurements do not unambiguously characterize the aerosol dry mass and composition which complicates the comparison with aerosol models. In this study we derive aerosol water and chemical composition by a modeling approach that combines individual measurements of remotely sensed aerosol properties (e.g. optical thickness, single scattering albedo, refractive index and size distribution) from an AERONET (Aerosol Robotic Network) sun-photometer with radiosonde measurements of relative humidity. The model simulates water uptake by aerosols based on the chemical composition and size distribution. A minimization method is used to calculate aerosol composition and concentration, which are then compared to in situ measurements from the Intensive Measurement Campaign At the Cabauw Tower (IMPACT, May 2008, the Netherlands). Computed concentrations show reasonable agreement with surface observations and follow the day-to-day variability in observations. Total dry mass (33 ± 12 μg m −3 ) and black carbon concentrations (0.7 ± 0.3 μg m −3 ) are generally accurately computed. The uncertainty in the AERONET (real) refractive index (0.025–0.05) introduces larger uncertainty in the modeled aerosol composition (e.g. sulfates, ammonium nitrate or organic matter) and leads to an uncertainty of 0.1–0.25 in aerosol water volume fraction. Water volume fraction is highly variable depending on composition, up to 〉0.5 at 70–80% and

Description: Technical note: Method of Morris effectively reduces the computational demands of global sensitivity analysis for distributed watershed models Hydrology and Earth System Sciences Discussions, 10, 4275-4299, 2013 Author(s): J. D. Herman, J. B. Kollat, P. M. Reed, and T. Wagener The increase in spatially distributed hydrologic modeling warrants a corresponding increase in diagnostic methods capable of analyzing complex models with large numbers of parameters. Sobol ' sensitivity analysis has proven to be a valuable tool for diagnostic analyses of hydrologic models. However, for many spatially distributed models, the Sobol ' method requires a prohibitive number of model evaluations to reliably decompose output variance across the full set of parameters. We investigate the potential of the method of Morris, a screening-based sensitivity approach, to provide results sufficiently similar to those of the Sobol ' method at a greatly reduced computational expense. The methods are benchmarked on the Hydrology Laboratory Research Distributed Hydrologic Model (HL-RDHM) model over a six-month period in the Blue River Watershed, Oklahoma, USA. The Sobol ' method required over six million model evaluations to ensure reliable sensitivity indices, corresponding to more than 30 000 computing hours and roughly 180 gigabytes of storage space. We find that the method of Morris is able to correctly identify sensitive and insensitive parameters with 300 times fewer model evaluations, requiring only 100 computing hours and 1 gigabyte of storage space. Method of Morris proves to be a promising diagnostic approach for global sensitivity analysis of highly parameterized, spatially distributed hydrologic models.

Description: Evaluation of various methods to measure particulate bound mercury and associated artifacts Atmospheric Chemistry and Physics Discussions, 13, 8585-8614, 2013 Author(s): S. Wang, T. M. Holsen, J. Huang, and Y.-J. Han This study was performed to determine how sampling artifacts associated with various sampling methods including open faced filter (OFF) pack, micro orifice uniform deposit impactor (MOUDI), and Tekran speciation system (TekSpec) impact particulate bound mercury (PBM) measurements. PBM measured by the MOUDI for 48 h was statistically lower than that measured with the TekSpec every 2 h, indicating that negative artifacts were significant for long sampling durations. Negative artifacts were also identified in lab experiments as the Hg 0 and HgCl 2 concentrations associated with particulate matter on the filter significantly decreased when the filter was exposed to zero air. Positive artifacts were also investigated. The OFF sampling for 48 h, which is likely to be associated with both positive and negative artifacts, measured a significantly lower PBM concentration than the TekSpec while the OFF and MOUDI (48 h sampling – minimal positive artifacts) showed similar results, suggesting that positive artifacts were minor under the rural condition encountered (low atmospheric gaseous oxidized mercury and typical oxidants concentrations). The Hg speciation associated with particles varied with atmospheric temperature, with the contribution of less volatile species including HgO and HgS increasing and more volatile Hg 0 and HgCl 2 decreasing as atmospheric temperature increased. There was significant correlation for PBM larger than 2.5 μm between TekSpec frit and MOUDI in this study, indicating that TekSpec frit is a good alternative sampler for measuring the concentration of coarse PBM.

Description: Aerosol and precipitation chemistry in the southwestern United States: spatiotemporal trends and interrelationships Atmospheric Chemistry and Physics Discussions, 13, 8615-8662, 2013 Author(s): A. Sorooshian, T. Shingler, A. Harpold, C. W. Feagles, T. Meixner, and P. D. Brooks This study characterizes the spatial and temporal patterns of aerosol and precipitation composition at six sites across the United States Southwest between 1995 and 2010. Precipitation accumulation occurs mostly during the wintertime (December–February) and during the monsoon season (July–September). Rain and snow pH levels are usually between 5–6, with crustal-derived species playing a major role in acid neutralization. These species (Ca 2+ , Mg 2+ , K + ,Na + ) exhibit their highest concentrations between March and June in both PM 2.5 and precipitation due mostly to dust. Crustal-derived species concentrations in precipitation exhibit positive relationships with SO 4 2− , NO 3 − , and Cl − , suggesting that acidic gases likely react with and partition to either crustal particles or hydrometeors enriched with crustal constituents. Concentrations of particulate SO 4 2− show a statistically significant correlation with rain SO 4 2− unlike snow SO 4 2− , which may be related to some combination of the vertical distribution of SO 4 2− (and precursors) and the varying degree to which SO 4 2− -enriched particles act as cloud condensation nuclei versus ice nuclei in the region. The coarse : fine aerosol mass ratio was correlated with crustal species concentrations in snow unlike rain, suggestive of a preferential role of coarse particles (mainly dust) as ice nuclei in the region. Precipitation NO 3 − : SO 4 2− ratios exhibit the following features with potential explanations discussed: (i) they are higher in precipitation as compared to PM 2.5 ; (ii) they exhibit the opposite annual cycle compared to particulate NO 3 − : SO 4 2− ratios; and (iii) they are higher in snow relative to rain during the wintertime. Long-term trend analysis for the monsoon season shows that the NO 3 − : SO 4 2− ratio in rain decreased at the majority of sites due mostly to air pollution regulations of SO 4 2− precursors.

Description: Effects of relative humidity on aerosol light scattering: results from different European sites Atmospheric Chemistry and Physics Discussions, 13, 8939-8984, 2013 Author(s): P. Zieger, R. Fierz-Schmidhauser, E. Weingartner, and U. Baltensperger The effect of aerosol water uptake on the aerosol particle light scattering coefficient (σ sp ) is described in this study by comparing measurements from five European sites: the Jungfraujoch, located in the Swiss Alps at 3580 m a.s.l., Ny-Ålesund, located on Spitsbergen in the Arctic, Mace Head, a coastal site in Ireland, Cabauw, a rural site in the Netherlands and Melpitz, a regional background site in Eastern Germany. These sites were selected according to the aerosol type usually encountered at that location. The scattering enhancement factor f (RH,λ) is the key parameter to describe the effect of water uptake on the particle light scattering. It is defined as the σ sp (RH) at a certain relative humidity (RH) and wavelength λ divided by its dry value. f (RH) largely varied at the five sites starting from very low values of f (RH = 85%,λ = 550 nm) around 1.28 for mineral dust to 3.41 for Arctic aerosol. Hysteresis behavior was observed at all sites except at the Jungfraujoch due to the absence of sea salt. Closure studies and Mie simulations showed that both size and chemical composition determine the magnitude of f (RH). Both parameters are also needed to successfully predict f (RH). Finally, the measurement results were compared to the widely used aerosol model OPAC (Hess et al., 1998). Significant discrepancies were seen especially at intermediate RH ranges, which were mainly attributed to inappropriate implemented hygroscopic growth within OPAC. Replacement of the hygroscopic growth with recent literature values showed a clear improvement of the OPAC model.

Description: Socio-hydrology: conceptualising human-flood interactions Hydrology and Earth System Sciences Discussions, 10, 4515-4536, 2013 Author(s): G. Di Baldassarre, A. Viglione, G. Carr, L. Kuil, J. L. Salinas, and G. Blöschl Over history, humankind has tended to settle near streams because of the role of rivers as transportation corridors and the fertility of riparian areas. However, human settlements in floodplains have been threatened by the risk of flooding. Possible responses have been to resettle away and/or modify the river system by building flood control structures. This has led to a complex web of interactions and feedback mechanisms between hydrological and social processes in settled floodplains. This paper is an attempt to conceptualise these interplays for hypothetical human-flood systems. We develop a simple, dynamic model to represent the interactions and feedback loops between hydrological and social processes. The model is then used to explore the dynamics of the human-flood system and the effect of changing individual characteristics, including external forcing such as technological development. The results show that the conceptual model is able to reproduce reciprocal effects between floods and people as well as the emergence of typical patterns. For instance, when levees are built or raised to protect floodplain areas, their presence not only reduces the frequency of flooding, but also exacerbates high water levels. Then, because of this exacerbation, higher flood protection levels are required by the society. As a result, more and more flooding events are avoided, but rare and catastrophic events take place.

Description: Integration of remote sensing, RUSLE and GIS to model potential soil loss and sediment yield (SY) Hydrology and Earth System Sciences Discussions, 10, 4567-4596, 2013 Author(s): H. Kamaludin, T. Lihan, Z. Ali Rahman, M. A. Mustapha, W. M. R. Idris, and S. A. Rahim Land use activities within a basin serve as one of the contributing factors which cause deterioration of river water quality through its potential effect on erosion. Sediment yield in the form of suspended solid in the river water body which is transported to the coastal area occurs as a sign of lowering of the water quality. Hence, the aim of this study was to determine potential soil loss using the Revised Universal Soil Loss Equation (RUSLE) model and the sediment yield, in the Geographical Information Systems (GIS) environment within selected sub-catchments of Pahang River Basin. RUSLE was used to estimate potential soil losses and sediment yield by utilizing information on rainfall erosivity ( R ) using interpolation of rainfall data, soil erodibility ( K ) using field measurement and soil map, vegetation cover ( C ) using satellite images, topography (LS) using DEM and conservation practices ( P ) using satellite images. The results indicated that the rate of potential soil loss in these sub-catchments ranged from very low to extremely high. The area covered by very low to low potential soil loss was about 99%, whereas moderate to extremely high soil loss potential covered only about 1% of the study area. Sediment yield represented only 1% of the potential soil loss. The sediment yield (SY) value in Pahang River turned out to be higher closer to the river mouth because of the topographic character, climate, vegetation type and density, and land use within the drainage basin.

Description: Probability distributions for explaining hydrological losses in South Australian catchments Hydrology and Earth System Sciences Discussions, 10, 4597-4626, 2013 Author(s): S. H. P. W. Gamage, G. A. Hewa, and S. Beecham The wide variability of hydrological losses in catchments is due to multiple variables that affect the rainfall-runoff process. Accurate estimation of hydrological losses is required for making vital decisions in design applications that are based on design rainfall models and rainfall-runoff models. Using representative single values of losses, despite their wide variability, is common practice, especially in Australian studies. This practice leads to issues such as over or under estimation of design floods. Probability distributions can be used as a better representation of losses. In particular, using joint probability approaches (JPA), probability distributions can be incorporated into hydrological loss parameters in design models. However, lack of understanding of loss distributions limits the benefit of using JPA. The aim of this paper is to identify a probability distribution function that can successfully describe hydrological losses in South Australian (SA) catchments. This paper describes suitable parametric and non-parametric distributions that can successfully describe observed loss data. The goodness-of-fit of the fitted distributions and quantification of the errors associated with quantile estimation are also discussed a two-parameter Gamma distribution was identified as one that successfully described initial loss (IL) data of the selected catchments. Also, a non-parametric standardised distribution of losses that describes both IL and continuing loss (CL) data were identified. The results obtained for the non-parametric methods were compared with similar studies carried out in other parts of Australia and a remarkable degree of consistency was observed. The results will be helpful in improving design flood applications.

Description: Spectro-microscopic measurements of carbonaceous aerosol aging in Central California Atmospheric Chemistry and Physics Discussions, 13, 9179-9216, 2013 Author(s): R. C. Moffet, T. C. Rödel, S. T. Kelly, X. Y. Yu, G. T. Carroll, J. Fast, R. A. Zaveri, A. Laskin, and M. K. Gilles Carbonaceous aerosols are responsible for large uncertainties in climate models, degraded visibility, and adverse health effects. The Carbonaceous Aerosols and Radiative Effects Study (CARES) was designed to study carbonaceous aerosols in the natural environment of Central Valley, California, and learn more about their atmospheric formation and aging. This paper presents results from spectro-microscopic measurements of carbonaceous particles collected during CARES at the time of pollution accumulation event (27–29 June 2010), when in situ measurements indicated an increase in the organic carbon content of aerosols as the Sacramento urban plume aged. Computer controlled scanning electron microscopy coupled with an energy dispersive X-ray detector (CCSEM/EDX) and scanning transmission X-ray microscopy coupled with near edge X-ray absorption spectroscopy (STXM/NEXAFS) were used to probe the chemical composition and morphology of individual particles. It was found that the mass of organic carbon on individual particles increased through condensation of secondary organic aerosol. STXM/NEXAFS indicated that the number fraction of homogenous organic particles lacking inorganic inclusions (greater than ~50 nm diameter) increased with plume age as did the organic mass per particle. Comparison of the CARES spectro-microscopic data set with a similar dataset obtained in Mexico City during the MILAGRO campaign showed that individual particles in Mexico City contained twice as much carbon as those sampled during CARES. The number fraction of soot particles at the Mexico City urban site (30%) was larger than at the CARES urban site (10%) and the most aged samples from CARES contained less carbon-carbon double bonds. Differences between carbonaceous particles in Mexico City and California result from different sources, photochemical conditions, gas phase reactants, and secondary organic aerosol precursors. The detailed results provided by these spectro-microscopic measurements will allow for a comprehensive evaluation of aerosol process models used in climate research.

Description: Technical Note: Using wavelet analyses on water depth time series to detect glacial influence in high-mountain hydrosystems Hydrology and Earth System Sciences Discussions, 10, 4369-4395, 2013 Author(s): S. Cauvy-Fraunié, T. Condom, A. Rabatel, M. Villacis, D. Jacobsen, and O. Dangles Worldwide, the rapid shrinking of glaciers in response to ongoing climate change is currently modifying the glacial meltwater contribution to hydrosystems in glacierized catchments. Assessing the contribution of glacier run-off to stream discharge is therefore of critical importance to evaluate potential impact of glacier retreat on water quality and aquatic biota. This task has challenged both glacier hydrologists and ecologists over the last 20 yr due to both structural and functional complexity of the glacier-stream system interface. Here we propose a new methodological approach based on wavelet analyses on water depth time series to determine the glacial influence in glacierized catchments. We performed water depth measurement using water pressure loggers over ten months in 15 stream sites in two glacier-fed catchments in the Ecuadorian Andes (〉 4000 m). We determined the global wavelet spectrum of each time series and defined the Wavelet Glacier Signal (WGS) as the ratio between the global wavelet power spectrum value at a 24 h-scale and its corresponding significance value. To test the relevance of the WGS we compared it with the percentage of the glacier cover in the catchments, a metric of glacier influence often used in the literature. We then tested whether one month data could be sufficient to reliably determine the glacial influence. As expected we found that the WGS of glacier-fed streams decreased downstream with the increasing of non-glacial tributaries. We also found that the WGS and the percentage of the glacier cover in the catchment were significantly positively correlated and that one month data was sufficient to identify and compare the glacial influence between two sites, provided that the water level time series were acquired over the same period. Furthermore, we found that our method permits to detect glacial signal in supposedly non-glacial sites, thereby evidencing glacial meltwater infiltrations. While we specifically focused on the tropical Andes in this paper, our approach to determine glacier influence would be applicable to temperate and arctic glacierized catchments. The WGS therefore appears as a powerful and cost effective tool to better understand the hydrological links between glaciers and hydrosystems and assess the consequences of rapid glacier melting.

Description: Spatio-temporal heterogeneity of riparian soil morphology in a restored floodplain Hydrology and Earth System Sciences Discussions, 10, 4337-4367, 2013 Author(s): B. Fournier, C. Guenat, G. Bullinger-Weber, and E. A. D. Mitchell Floodplains have been intensively altered in industrialized countries, but are now increasingly being restored and it is therefore important to assess the effect of these restoration projects on the aquatic and terrestrial components of ecosystems. Soils are a functionally crucial component of terrestrial ecosystems but are generally overlooked in floodplain restoration assessment. We studied the spatio-temporal heterogeneity of soil morphology in a restored (riverbed widening) river reach along River Thur (Switzerland) using three criteria (soil diversity, dynamism and typicality) and their associated indicators. We hypothesized that these criteria would correctly discriminate the post-restoration changes in soil morphology within the study site, and that these changes correspond to patterns of vascular plant diversity. Soil diversity and dynamism increased five years after the restoration, but typical soils of braided rivers were still missing. Soil typicality and dynamism correlated to vegetation changes. These results suggest a limited success of the project in agreement with evaluations carried out at the same site using other, more resource demanding methods (e.g. soil fauna, fish, ecosystem functioning). Soil morphology provides structural and functional information on floodplain ecosystems and allows predicting broad changes in plant diversity. The spatio-temporal heterogeneity of soil morphology represents a cost-efficient ecological indicator that could easily be integrated into rapid assessment protocols of floodplain and river restoration projects.

Description: Space-time kriging extension of precipitation variability at 12 km spacing from tree-ring chronologies and its implications for drought analysis Hydrology and Earth System Sciences Discussions, 10, 4301-4335, 2013 Author(s): F. Biondi Understanding and preparing for future hydroclimatic variability greatly benefits from long (i.e., multi-century) records at seasonal to annual time steps that have been gridded at km-scale spatial intervals over a geographic region. Kriging is a geostatistical technique commonly used for optimal interpolation of environmental data, and space-time geostatistical models can improve kriging estimates when long temporal sequences of observations exist at relatively few points on the landscape. Here I present how a network of 22 tree-ring chronologies from single-leaf pinyon ( Pinus monophylla ) in the central Great Basin of North America was used to extend hydroclimatic records both temporally and spatially. First, the Line of Organic Correlation (LOC) method was used to reconstruct October–May total precipitation anomalies at each tree-ring site, as these ecotonal environments at the lower forest border are typically moisture limited. Individual site reconstructions were then combined using a hierarchical model of spatio-temporal kriging that produced annual anomaly maps on a 12 × 12 km grid during the period in common among all chronologies (1650–1976). Hydro-climatic episodes were numerically identified and modeled using their duration, magnitude, and peak. Spatial patterns were more variable during wet years than during dry years, and the evolution of drought episodes over space and time could be visualized and quantified. The most remarkable episode in the entire reconstruction was the early 1900s pluvial, followed by the late 1800s drought. The 1930s "Dust Bowl" drought was among the top ten hydroclimatic episodes in the past few centuries. These results directly address the needs of water and natural resource managers with respect to planning for "worst case" scenarios of drought duration and magnitude at the watershed level. For instance, it is possible to analyze which geographical areas are more likely to be impacted by severe and sustained droughts at annual or multiannual timescales and at spatial resolutions commonly used by regional climate models.

Description: Laboratory studies of immersion and deposition mode ice nucleation of ozone aged mineral dust particles Atmospheric Chemistry and Physics Discussions, 13, 8701-8767, 2013 Author(s): Z. A. Kanji, A. Welti, C. Chou, O. Stetzer, and U. Lohmann Ice nucleation in the atmosphere is central to the understanding the microphysical properties of mixed-phase and cirrus clouds. Ambient conditions such as temperature ( T ) and relative humidity (RH), as well as aerosol properties such as chemical composition and mixing state play an important role in predicting ice formation in the troposphere. Previous field studies have reported the absence of sulphate and organic compounds on mineral dust ice crystal residuals sampled at mountain top stations or aircraft based measurements despite the long range transport mineral dust is subjected to. We present laboratory studies of ice nucleation for immersion and deposition mode on ozone aged mineral dust particles for 233 〈 T 〈 263 K that will represent ageing but not internal mixing with in(organic) compounds. Heterogeneous ice nucleation of untreated kaolinite (Ka) and Arizona Test Dust (ATD) particles is compared to corresponding aged particles that are subjected to ozone exposures of 0.4–4.3 ppmv in a stainless steel aerosol tank. The portable ice nucleation counter (PINC) and immersion chamber combined with the Zurich ice nucleation chamber (IMCA – ZINC) are used to conduct deposition and immersion mode measurements respectively. Ice active fractions as well as ice active surface site densities ( n s ) are reported and observed to increase as a function of temperature. We present first results that demonstrate enhancement of the ice nucleation ability of aged mineral dust particles in both the deposition and immersion mode due to ageing. Additionally, these are also the first results to show a suppression of heterogeneous ice nucleation without the condensation of a coating of (in)organic material. In immersion mode, low exposure Ka particles showed enhanced ice activity requiring a median freezing temperature of 1.5 K warmer than that of untreated Ka whereas high exposure ATD particles showed suppressed ice nucleation requiring a median freezing temperature of 3 K colder than that of untreated ATD. In deposition mode, low exposure Ka had ice active fractions of an order of magnitude higher than untreated Ka, where as high exposure ATD had ice active fractions up to a factor of 4 lower than untreated ATD. Based on our results, we present parameterizations in terms of n s ( T ) that can represent ice nucleation of atmospherically aged and non-aged particles for both immersion and deposition mode. We find excellent agreement (to within less than a factor of 2) with field measurements when parameterizations derived from our results are used to predict ice nuclei concentrations in the troposphere.

Description: Retrieval of the Eyjafjallajökull volcanic aerosol optical and microphysical properties from POLDER/PARASOL measurements Atmospheric Chemistry and Physics Discussions, 13, 8663-8699, 2013 Total and polarized radiances provided by the Polarization and Directionality of Earth Reflectances (POLDER) satellite sensor are used to retrieve the microphysical and optical properties of the volcanic plume observed during the Eyjafjallajökull volcano eruption in 2010, over cloud-free and cloudy ocean scenes. We selected two plume conditions, fresh aerosols near the sources (three cases) and a downwind volcanic plume observed over the North Sea 30 h after its injection into the atmosphere (aged aerosols). In the near-source conditions, the aerosol properties depend on the distance to the plume. Within the plume, aerosols are mainly non-spherical and in the coarse mode with an effective radius equal to 1.50 (± 0.15) μm and an Ångström Exponent (AE) close to 0.0. Far from the plume, in addition to the coarse mode, there are smaller particles retrieved in the accumulation mode suggesting a mixture of sulfate aerosols and volcanic dust, resulting in an AE around 0.8. The properties of the aerosols also depend on whether the plume is fresh or aged. For the downwind (aged) plume, if non-spherical coarse particles as well as some fine mode particles are still retrieved, the AE is smaller, around ~ 0.4. In addition, the real refractive index (RR) values are larger for the downwind plume (1.42 〈 RR 〈 1.58) than for the near-source plume (1.38 〈 RR 〈 1.48). The mean Single Scattering Albedo (SSA) retrieved at 0.865 μm was estimated at 0.97 over some parts of the downwind and near-source plumes; despite the low accuracy of our retrievals, the derived SSA values suggest that the ash particles are rather absorbing. To consider the particle shape, a combination of spheroid models is used. Although the employed model enabled accurate modeling of the POLDER signal in case of non-spherical ash, our approach failed to model the signal over the optically thickest parts of the near-source plume. The most probable reason for this is speculated to be the presence of ice crystals within the plume. For the Aerosol Above Clouds (AAC) scenes, polarized measurements allowed the retrieval of the Optical Thickness (OT) and the AE of optically thin volcanic ash. We found that all the cloud parameters retrieved by passive sensors were biased due to the presence of the elevated volcanic plumes. Finally, thermal infrared measurements were used to identify the type of multi-layer scene (i.e. cirrus clouds or volcanic dust above liquid clouds) and the retrieval method also provided the OT of thin cirrus layers above the clouds near Iceland.

Description: Optimising predictor domains for spatially coherent precipitation downscaling Hydrology and Earth System Sciences Discussions, 10, 4015-4061, 2013 Author(s): S. Radanovics, J.-P. Vidal, E. Sauquet, A. Ben Daoud, and G. Bontron Statistical downscaling is widely used to overcome the scale gap between predictors from Numerical Weather Prediction (NWP) models or General Circulation Models (GCMs) and predictands like local precipitation, required for example for medium-term operational forecasts or climate change impact studies. The predictors are considered over a given spatial domain which is rarely optimised with respect to the target predictand location. In this study the geopotential predictor domains used by an analogue downscaling method are optimised for 608 target zones covering France. An extended version of the growing rectangular domain algorithm provides an ensemble of five near-optimum domains for each target zone. All five near-optimum domains are consistently equally skillful based on the Continuous Rank Probability Score. Relevance maps calculated for selected target zones first reveal high skill geopotential regions with specific shapes for locations in south-eastern France compared to the rest of the country. In all cases, the optimised domains tend to include the most relevant area on the relevance maps. The domain centers of the optimised domains are mainly distributed following the geographical location of the target location, but there are apparent differences between the windward and the lee side of mountain ridges. Moreover, domains for target zones located in south-eastern France are centered more east and south than the ones for target locations on the same longitude. The size of the optimised domains tends to be larger in the southeastern part of the country, while domains with a very small meridional extent can be found in a east-west band around 47° N. Sensitivity tests on the archive length for the analogue method show a general robustness except for zones with high interannual variability like in the Cévennes area. Moreover, results appear to be rather unsensitive to the starting point of the optimisation algorithm except for zones located in the transition area north of the zones having optimized domains with a small meridional extent. This study paves the way for defining regions with homogeneous geopotential predictor domains for precipitation downscaling over France.

Description: Opportunities and challenges for the use of scintillometer-based catchment-averaged evapotranspiration estimates as model forcing Hydrology and Earth System Sciences Discussions, 10, 3973-4013, 2013 Author(s): B. Samain and V. R. N. Pauwels To date, lumped rainfall-runoff models rely on rough estimates of catchment-averaged potential evapotranspiration (ET p ) rates as meteorological forcing. A model parameter converts this ET p input into actual evapotranspiration (ET act ) estimates. This paper examines the potential use of scintillometer-based ET act rates for rainfall-runoff modeling. It has been found that the reservoir-structure of the rainfall-runoff model functions as a low-pass filter for the ET p input. If the long-term volume of the ET p used in the model simulations is consistent with the data set used for calibration, a good match of the seasonal pattern, using temporally constant ET p data, is sufficient to obtain adequate discharge simulations. However, these results are then obtained with strongly erroneous evapotranspiration estimates. A better match of the diurnal cycle does not lead to better model results. Replacing the ET p inputs by scintillometer-based ET act estimates does not lead to better model predictions. Small underestimations of ET act under stable conditions, which occur at night and during the Winter, and which accumulate to significant amounts, are the cause of this problem. Consistent with other studies, the scintillometer-based ET act estimates can be considered reliable and realistic under unstable conditions. These values can thus be used as forcing for rainfall-runoff models.

Description: Temporal stability of soil moisture patterns measured by proximal ground-penetrating radar Hydrology and Earth System Sciences Discussions, 10, 4063-4097, 2013 Author(s): J. Minet, N. E. C. Verhoest, S. Lambot, and M. Vanclooster We analyzed the temporal stability of soil moisture patterns acquired using a proximal ground-penetrating radar (GPR) in a 2.5 ha agricultural field at five different dates over three weeks. The GPR system was mounted on a mobile platform, allowing for real-time mapping of soil moisture with a high spatial resolution (2–5 m). The spatio-temporal soil moisture patterns were in accordance with the meteorological data and with soil moisture measurements from soil core sampling. Time-stable areas showing the field-average moisture could be revealed by two methods: (1) by the computation of temporal stability indicators based on relative differences of soil moisture to the field-average and (2) by the spatial intersection of the areas showing the field-average. Locations where the mean relative difference was below 0.02 m 3 m −3 extended up to 10% of the field area whereas the intersection of areas showing the field-average within a tolerance of 0.02 m 3 m −3 covered 5% of the field area. Compared to most of the previous studies about temporal stability of soil moisture, time-stable areas and their spatial patterns could be revealed instead of single point locations, owing to the advanced GPR method for real-time mapping. It is believed that determining spatially coherent time-stable areas is more informative rather than determining time-stable points. Other acquisitions over larger time periods would be necessary to assert the robustness of the time-stable areas.

Description: Present and future nitrogen deposition to national parks in the United States: critical load exceedances Atmospheric Chemistry and Physics Discussions, 13, 9151-9178, 2013 Author(s): R. A. Ellis, D. J. Jacob, M. Payer, L. Zhang, C. D. Holmes, B. A. Schichtel, T. Blett, E. Porter, L. H. Pardo, and J. A. Lynch National parks in the United States are protected areas wherein the natural habitat is to be conserved for future generations. Deposition of anthropogenic nitrogen (N) transported from areas of human activity (fuel combustion, agriculture) may affect these natural habitats if it exceeds an ecosystem-dependent critical load (CL). We quantify and interpret the deposition to Class I US national parks for present-day and future (2050) conditions using the GEOS-Chem global chemical transport model with 1/2° × 2/3° horizontal resolution over North America. We estimate CL values in the range 2.5–5 kg N ha −1 yr −1 for the different parks with the goal of protecting the most sensitive ecosystem receptors. For present-day conditions, we find 24 out of 45 parks to be in CL exceedance and 14 more to be marginally so. Many of these are in remote areas of the West. Most (40–85%) of the deposition originates from NO x emissions (fuel combustion). We then project future changes in N deposition using the Representative Concentration Pathway (RCP) emission scenarios for 2050. These feature 52–73% declines in US NO x emissions relative to present but 19–50% increases in US ammonia (NH 3 ) emissions. Nitrogen deposition at US national parks then becomes dominated by domestic NH 3 emissions. While deposition decreases in the East relative to present, there is little progress in the West and increases in some regions. We find that 17–25 US national parks will have CL exceedances in 2050 based on the RCP scenarios. Even in total absence of anthropogenic NO x emissions, 14–18 parks would still have a CL exceedance. Returning all parks to N deposition below CL by 2050 will require at least a 55% decrease in anthropogenic NH 3 emissions relative to RCP-projected 2050 levels.

Description: Redox activity of naphthalene secondary organic aerosol Atmospheric Chemistry and Physics Discussions, 13, 9107-9149, 2013 Author(s): R. D. McWhinney, S. Zhou, and J. P. D. Abbatt Chamber secondary organic aerosol (SOA) from low-NO x photooxidation of naphthalene by hydroxyl radical was examined with respect to its redox cycling behaviour using the dithiothreitol (DTT) assay. Naphthalene SOA was highly redox active, consuming DTT at an average rate of 118 ± 14 pmol per minute per μg of SOA material. Measured particle-phase masses of the major previously identified redox active products, 1,2- and 1,4-naphthoquinone, accounted for only 21 ± 3% of the observed redox cycling activity. The redox-active 5-hydroxy-1,4-naphthoquinone was identified as a new minor product of naphthalene oxidation, and including this species in redox activity predictions increased the predicted DTT reactivity to 30 ± 5% of observations. Similar attempts to predict redox behaviour of oxidised two-stroke engine exhaust particles by measuring 1,2-naphthoquinone, 1,4-naphthoquinone and 9,10-phenanthrenequinone predicted DTT decay rates only 4.9 ± 2.5% of those observed. Together, these results suggest that there are substantial unidentified redox-active SOA constituents beyond the small quinones that may be important toxic components of these particles. A gas-to-SOA particle partitioning coefficient was calculated to be (7.0 ± 2.5) × 10 −4 m 3 μg −1 for 1,4-naphthoquinone at 25 °C. This value suggests that under typical warm conditions, 1,4-naphthoquinone is unlikely to contribute strongly to redox behaviour of ambient particles, although further work is needed to determine the potential impact under conditions such as low temperatures where partitioning to the particle is more favourable. As well, higher order oxidation products that likely account for a substantial fraction of the redox cycling capability of the naphthalene SOA are likely to partition much more strongly to the particle phase.

Description: Impacts of tropical cyclones on hydrochemistry of a subtropical forest Hydrology and Earth System Sciences Discussions, 10, 4537-4566, 2013 Author(s): C. T. Chang, S. P. Hamburg, J. L. Hwong, N. H. Lin, M. L. Hsueh, M. C. Chen, and T. C. Lin Tropical cyclones (typhoons/hurricanes) have major impacts on the biogeochemistry of forest ecosystems, but the stochastic nature and the long intervals between storms means that there are limited data on their effects. We characterized the impacts of 14 typhoons over six years on hydrochemistry of a subtropical forest plantation in Taiwan, a region experiencing frequent typhoons. Typhoons contributed 1/3 of annual rainfall on average, but ranged from 4% to 55%. The stochastic nature of annual typhoon related precipitation poses a challenge with respect to managing the impacts of these extreme events. This challenge is exacerbated by the fact that typhoon-related rainfall is not significantly correlated with wind velocity, the current focus of weather forecasts. Thus little advance warning is provided for the hydrological impacts of these storms. The typhoons we studied contributed approximately one third of the annual input and output of most nutrients (except nitrogen) during an average 9.5d yr −1 period, resulting in nutrient input/output rates an order of magnitude greater than during non-typhoon period. Nitrate output balanced input during the non-typhoon period, but during the typhoon period an average of 10 kg ha −1 yr −1 nitrate was lost. Streamwater chemistry exhibited similarly high variability during typhoon and non-typhoon periods and returned to pre-typhoon levels one to three weeks following each typhoon. The streamwater chemistry appears to be very resilient in response to typhoons, resulting in minimal loss of nutrients.

Description: Factors that influence surface PM 2.5 values inferred from satellite observations: perspective gained for the Baltimore-Washington Area during DISCOVER-AQ Atmospheric Chemistry and Physics Discussions, 13, 23421-23459, 2013 Author(s): S. Crumeyrolle, G. Chen, L. Ziemba, A. Beyersdorf, L. Thornhill, E. Winstead, R. Moore, M. A. Shook, and B. Anderson During the NASA DISCOVER-AQ campaign over the Washington D.C., - Baltimore, MD, metropolitan region in July 2011, the NASA P-3B aircraft performed extensive profiling of aerosol optical, chemical, and microphysical properties. These in-situ profiles were coincident with ground based remote sensing (AERONET) and in-situ (PM 2.5 ) measurements. Here, we use this data set to study the correlation between the PM 2.5 observations at the surface and the column integrated measurements. Aerosol optical depth (AOD) calculated with the extinction (532 nm) measured during the in-situ profiles was found to be strongly correlated with the volume of aerosols present in the boundary layer (BL). Despite the strong correlation, some variability remains, and we find that the presence of aerosol layers above the BL (in the buffer layer – BuL) introduces a significant uncertainties in PM 2.5 estimates based on column-integrated measurements. This motivates the use of active remote sensing techniques to dramatically improve air quality retrievals. Since more than a quarter of the AOD values observed during DISCOVER-AQ are dominated by aerosol water uptake, the f (RH) amb (obtained from two nephelometers at different relative humidities – RHs) is used to study the impact of the aerosol hygroscopicity. The results indicate that PM 2.5 can be predicted within a factor of 1.6 even when the vertical variability of the f (RH) amb is assumed to be negligible.

Description: On clocks and clouds Atmospheric Chemistry and Physics Discussions, 13, 23461-23490, 2013 Author(s): M. K. Witte, P. Y. Chuang, and G. Feingold Cumulus clouds exhibit a life cycle that consists of: (a) the growth phase (increasing size, most notably in the vertical direction); (b) the mature phase (growth ceases; any precipitation that develops is strongest during this period); and (c) the dissipation phase (cloud dissipates because of precipitation and/or entrainment; no more dynamical support). Although radar can track clouds over time and give some sense of the age of a cloud, most aircraft in situ measurements lack temporal context. We use large eddy simulations of trade wind cumulus cloud fields from cases during the Barbados Oceanographic and Meteorological Experiment (BOMEX) and Rain In Cumulus over the Ocean (RICO) campaigns to demonstrate a potential cumulus cloud "clock". We find that the volume-averaged total water mixing ratio r t is a useful cloud clock for the 12 clouds studied. A cloud's initial r t is set by the subcloud mixed-layer mean r t and decreases monotonically from the initial value due primarily to entrainment. The clock is insensitive to aerosol loading, environmental sounding and extrinsic cloud properties such as lifetime and volume. In some cases (more commonly for larger clouds), multiple pulses of buoyancy occur, which complicate the cumulus clock by replenishing r t . The clock is most effectively used to classify clouds by life phase.

Description: Assessment of the effect of air pollution controls on trends in shortwave radiation over the United States from 1995 through 2010 from multiple observation networks Atmospheric Chemistry and Physics Discussions, 13, 23719-23755, 2013 Author(s): C.-M. Gan, J. Pleim, R. Mathur, C. Hogrefe, C. N. Long, J. Xing, S. Roselle, and C. Wei Long term datasets of all-sky and clear-sky downwelling shortwave (SW) radiation, cloud cover fraction and aerosol optical depth (AOD) are analyzed together with surface concentration from several networks (e.g. SURFRAD, CASTNET, IMPROVE and ARM) in the United States (US). Seven states with varying climatology are selected to better understand the effects of aerosols and clouds on SW radiation. This analysis aims to assess the effects of reductions in anthropogenic aerosol burden resulting from substantial reductions in emissions of sulfur dioxide (SO 2 ) and nitrogen oxides (NO x ) over the past 16 yr across the US on trends in SW radiation. The SO 2 and NO x emission data show decreasing trends from 1995 to 2010 which indirectly validates the effects of the Clean Air Act (CAA) in the US. Meanwhile, the total column AOD and surface total PM 2.5 observations also show decreasing trends in the eastern US but slightly increasing trends in the western US. Moreover, measured surface concentrations of several other pollutants (i.e. SO 2 , SO 4 and NO x ) have the same behavior as the AOD and total PM 2.5 . First, all-sky downwelling SW radiation is assessed together with the cloud cover. Results of this analysis show strong increasing trends in all-sky downwelling SW radiation with decreasing trends in cloud cover. However, since observations of both all-sky direct and diffuse SW radiation are increasing, there may be other factors contributing to the radiation trends in addition to the decreasing trends in overall cloud cover. To investigate the role of direct radiative effects of aerosols, clear-sky downwelling radiation is analyzed so that cloud effects are eliminated. However, similar increasing trends in clear-sky direct and diffuse SW radiation are observed. While significantly decreasing trends in AOD and surface concentration along with increasing SW radiation (both all-sky and clear-sky) in the eastern US during 1995–2010 imply the occurrence of direct aerosol mediated "brightening", the increasing trends of both all-sky and clear sky diffuse SW radiation contradicts this conclusion since diffuse radiation would be expected to decrease as aerosols direct effects decrease. After investigating several confounding factors, the increasing trend in diffuse SW may be due to more high-level cirrus from increasing air traffic over the US. In contrast to the eastern US, radiation observations in the western US do not show any indication of "brightening" which is consistent with the observations (e.g. AOD, PM 2.5 and surface concentration) that show the aerosol loading increasing slightly. This outcome is not unexpected because the CAA controls were mainly aimed at reducing air pollutants emission in the eastern US and air pollutant level in the western US are much lower.

Description: Modeled global effects of airborne desert dust on air quality and premature mortality Atmospheric Chemistry and Physics Discussions, 13, 24023-24050, 2013 Author(s): D. Giannadaki, A. Pozzer, and J. Lelieveld Fine particulate matter is one of the most important factors contributing to air pollution. Epidemiological studies have related increased levels of atmospheric particulate matter to premature human mortality caused by cardiopulmonary disease and lung cancer. However, a limited number of investigations have focused on the contribution of airborne desert dust particles. Here we assess the effects of dust particles with an aerodynamic diameter smaller than 2.5 μm (DU 2.5 ) on human mortality for the year 2005. We used the EMAC atmospheric chemistry general circulation model at high resolution to simulate global atmospheric dust concentrations. We applied a health impact function to estimate premature mortality for the global population of 30 yr and older, using parameters from epidemiological studies. We estimate a global cardiopulmonary mortality of about 402 thousand and about 10 thousand by lung cancer in 2005. The associated years of life lost are about 3.47 million and 96 thousand per year due to cardiopulmonary disease and lung cancer, respectively. We estimate the global fraction of the cardiopulmonary and lung cancer deaths caused by atmospheric desert dust to be about 1.7%, though in the 20 countries most affected by dust this is much higher, about 15–50%. These countries are primarily found in the so-called "dust belt" from North Africa across the Middle East and South Asia to East Asia.

Description: Aerosols optical and physical characteristics and direct radiative forcing during a "Shamal" dust storm, a case study Atmospheric Chemistry and Physics Discussions, 13, 23895-23941, 2013 Author(s): T. M. Saeed, H. Al-Dashti, and C. Spyrou Dust aerosols are analyzed for their optical and physical properties during an episode of dust storm that hit Kuwait on 26 March 2003 when "Iraqi Freedom" military operation was in full swing. The intensity of the dust storm was such that it left a thick suspension of dust throughout the following day, 27 March, resulting in a considerable cooling effect at the surface on both days. Ground-based measurements of aerosol optical thickness reached 3.617 and 4.17 on 26–27 March respectively while Ångstrom coefficient, α 870/440 , dropped to −0.0234 and −0.0318. Particulate matter concentration of diameter 10 μm or less, PM 10 , peaked at 4800 μg m −3 during dust storm hours of 26 March. Moderate resolution imaging spectrometer (MODIS) retrieved optical and physical characteristics that exhibited extreme values as well. The synoptic of the dust storm is presented and source regions are identified using total ozone mapping spectrometer (TOMS) aerosol index retrieved images. The vertical profile of the dust layer was simulated using SKIRON atmospheric model. Instantaneous net direct radiative forcing is calculated at top of atmosphere (TOA) and surface level. The thick dust layer of 26 March resulted in cooling the TOA by −60 Wm −2 and surface level by −175 Wm −2 for a surface albedo of 0.35. Slightly higher values were obtained for 27 March due to the increase in aerosol optical thickness. The large reduction in the radiative flux at the surface level had caused a drop in surface temperature by approximately 6 °C below its average value. Radiative heating/cooling rates in the shortwave and longwave bands were also examined. Shortwave heating rate reached a maximum value of 2 °K day −1 between 3 and 5 km, dropped to 1.5 °K day −1 at 6 km and diminished at 8 km. Longwave radiation initially heated the lower atmosphere by a maximum value of 0.2 °K day −1 at surface level, declined sharply at increasing altitude and diminished at 4 km. Above 4 km longwave radiation started to cool the atmosphere slightly reaching a maximum rate of −0.1 °K day −1 at 6 km.

Description: A scale and aerosol aware stochastic convective parameterization for weather and air quality modeling Atmospheric Chemistry and Physics Discussions, 13, 23845-23893, 2013 Author(s): G. A. Grell and S. R. Freitas A convective parameterization is described and evaluated that may be used in high resolution non-hydrostatic mesoscale models as well as in modeling systems with unstructured varying grid resolutions and for convection aware simulations. This scheme is based on a stochastic approach originally implemented by Grell and Devenyi (2002). Two approaches are tested on resolutions ranging from 20 to 5 km. One approach is based on spreading subsidence to neighboring grid points, the other one on a recently introduced method by Arakawa et al. (2011). Results from model intercomparisons, as well as verification with observations indicate that both the spreading of the subsidence and Arakawa's approach work well for the highest resolution runs. Because of its simplicity and its capability for an automatic smooth transition as the resolution is increased, Arakawa's approach may be preferred. Additionally, interactions with aerosols have been implemented through a CCN dependent autoconversion of cloud water to rain as well as an aerosol dependent evaporation of cloud drops. Initial tests with this newly implemented aerosol approach show plausible results with a decrease in predicted precipitation in some areas, caused by the changed autoconversion mechanism. This change also causes a significant increase of cloud water and ice detrainment near the cloud tops. Some areas also experience an increase of precipitation, most likely caused by strengthened downdrafts.

Description: Hurricane impacts on a pair of coastal forested watersheds: implications of selective hurricane damage to forest structure and streamflow dynamics Hydrology and Earth System Sciences Discussions, 10, 11519-11557, 2013 Author(s): A. D. Jayakaran, T. M. Williams, H. Ssegane, D. M. Amatya, B. Song, and C. C. Trettin Hurricanes are infrequent but influential disruptors of ecosystem processes in the southeastern Atlantic and Gulf coasts. Every southeastern forested wetland has the potential to be struck by a tropical cyclone. We examined the impact of Hurricane Hugo on two paired coastal watersheds in South Carolina in terms of stream flow and vegetation dynamics, both before and after the hurricane's passage in 1989. The study objectives were to quantify the magnitude and timing of changes including a reversal in relative streamflow-difference between two paired watersheds, and to examine the selective impacts of a hurricane on the vegetative composition of the forest. We related these impacts to their potential contribution to change watershed hydrology through altered evapotranspiration processes. Using over thirty years of monthly rainfall and streamflow data we showed that there was a significant transformation in the hydrologic character of the two watersheds – a transformation that occurred soon after the hurricane's passage. We linked the change in the rainfall-runoff relationship to a catastrophic shift in forest vegetation due to selective hurricane damage. While both watersheds were located in the path of the hurricane, extant forest structure varied between the two watersheds as a function of experimental forest management techniques on the treatment watershed. We showed that the primary damage was to older pines, and to some extent larger hardwood trees. We believe that lowered vegetative water use impacted both watersheds with increased outflows on both watersheds due to loss of trees following hurricane impact. However, one watershed was able to recover to pre hurricane levels of canopy transpiration at a quicker rate due to the greater abundance of pine seedlings and saplings in that watershed.

Description: Climatology of new particle formation events in the subtropical North Atlantic free troposphere at Izaña GAW observatory Atmospheric Chemistry and Physics Discussions, 13, 24127-24169, 2013 Author(s): M. I. García, S. Rodríguez, Y. González, and R. D. García A climatology of new particle formation (NPF) events in the subtropical North Atlantic free troposphere is presented. A four year data set (June 2008–June 2012), which includes number size distributions (10–600 nm), reactive gases (SO 2 , NO x , and O 3 ), several components of solar radiation and meteorological parameters, measured at Izaña Global Atmospheric Watch observatory (2400 m above sea level; Tenerife, Canary Islands) was analysed. On average, NPF occurred during 30% of the days,the mean values of the formation and growth rates during the study period were 0.49 cm −3 s −1 and 0.42 nm h −1 , correspondingly. There is a clearly marked NPF season (May to August), when these events account for 50 to 60% of the days/month. Monthly mean values of the formation and growth rates exhibit higher values during this season (0.50–0.95 cm −3 s −1 and 0.48–0.58 nm h −1 , respectively) than during other periods. The two steps (formation and growth) of the NPF process mostly occur under the prevailing northern winds typical of this region. Sulphur dioxide and UV radiation show higher levels during NPF events than in other type of episodes. The presence of Saharan dust in the free troposphere is associated with a decrease in the formation rates of new particles. In the analysis of the year-to-year variability, mean sulphur dioxide concentration (within the range 60–300 ppt) was the parameter that exhibited the highest correlation with the frequency of NPF episodes. The availability of this trace gas (i.e. their oxidation products) seems also to have a influence on the duration of the events, number of formed nucleation particles, formation rates and growth rates. We identified a set of NPF events in which two nucleation modes (that may evolve at different rates) occur simultaneously and for which further investigations are necessary.

Description: Numerical analysis of the chemical kinetic mechanisms of ozone depletion and halogen release in the polar troposphere Atmospheric Chemistry and Physics Discussions, 13, 24171-24222, 2013 Author(s): L. Cao, H. Sihler, U. Platt, and E. Gutheil In recent years, the role of halogen species (e.g. Br, Cl) in the troposphere of polar regions is investigated after the discovery of their importance for boundary layer ozone destruction in the polar spring. Halogen species take part in an auto-catalytic chemical cycle including key self reactions. In this study, several chemical reaction schemes are investigated, and the importance of specific reactions and their rate constants is identified by a sensitivity analysis. A category of heterogeneous reactions related to HOBr activate halogen ions from sea salt aerosols, fresh sea ice or snow pack, driving the "bromine explosion". In the Arctic, a small amount of NO x may exist, which comes from nitrate contained in the snow, and this NO x may have a strong impact on ozone depletion. The heterogeneous reaction rates are parameterized by considering the aerodynamic resistance, a reactive surface ratio, β, i.e. ratio of reactive surface area to total ground surface area, and the boundary layer height, L mix . It is found that for β = 1, the ozone depletion process starts after five days and lasts for 40 h for L mix = 200 m. Ozone depletion duration becomes independent of the height of the boundary layer for about β≥20, and it approaches a value of two days for β=100. The role of nitrogen and chlorine containing species on the ozone depletion rate is studied. The calculation of the time integrated bromine and chlorine atom concentrations suggests a value in the order of 10 3 for the [Br] / [Cl] ratio, which reveals that atomic chlorine radicals have minor direct influence on the ozone depletion. The NO x concentrations are influenced by different chemical cycles over different time periods. During ozone depletion, the reaction cycle involving the BrONO 2 hydrolysis is dominant. A critical value of 0.002 of the uptake coefficient of the BrONO 2 hydrolysis reaction at the aerosol and saline surfaces is identified, beyond which the existence of NO x species accelerate the ozone depletion event – for lower values, deceleration occurs.