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Aircraft borne optical in situ size distribution measurements were performed within Arctic boundary layer clouds with a special emphasis on the cloud top layer during the VERtical Distribution of Ice in Arctic clouds (VERDI) campaign in April and May 2012. An instrumented Basler BT-67 research aircraft operated out of Inuvik over the Mackenzie River delta and the Beaufort Sea in the Northwest Territories of Canada. Besides the cloud particle and hydrometeor size spectrometers the aircraft was equipped with instrumentation for aerosol, radiation and other parameters. Inside the cloud, droplet size distributions with monomodal shapes were observed for predominantly liquid-phase Arctic stratocumulus. With increasing altitude inside the cloud the droplet mean diameters grew from 10 to 20 μm. In the upper transition zone (i.e., adjacent to the cloud-free air aloft) changes from monomodal to bimodal droplet size distributions (Mode 1 with 20 μm and Mode 2 with 10 μm diameter) were observed. It is shown that droplets of both modes co-exist in the same (small) air volume and the bimodal shape of the measured size distributions cannot be explained as an observational artifact caused by accumulating data point populations from different air volumes. The formation of the second size mode can be explained by (a) entrainment and activation/condensation of fresh aerosol particles, or (b) by differential evaporation processes occurring with cloud droplets engulfed in different eddies. Activation of entrained particles seemed a viable possibility as a layer of dry Arctic enhanced background aerosol (which was detected directly above the stratus cloud) might form a second mode of small cloud droplets. However, theoretical considerations and model calculations (adopting direct numerical simulation, DNS) revealed that, instead, turbulent mixing and evaporation of larger droplets are the most likely reasons for the formation of the second droplet size mode in the uppermost region of the clouds.
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We present a HCN climatology of the years 2002–2012, derived from FTIR limb emission spectra measured with the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) on the ENVISAT satellite, with the main focus on biomass burning signatures in the upper troposphere and lower stratosphere. HCN is an almost unambiguous tracer of biomass burning with a tropospheric lifetime of 5–6 months and a stratospheric lifetime of about 2 years. The MIPAS climatology is in good agreement with the HCN distribution obtained by the spaceborne ACE-FTS experiment and with airborne in situ measurements performed during the INTEX-B campaign. The HCN amounts observed by MIPAS in the southern tropical and subtropical upper troposphere have an annual cycle peaking in October–November, i.e. 1–2 months after the maximum of southern hemispheric fire emissions. The probable reason for the time shift is the delayed onset of deep convection towards austral summer. Because of overlap of varying biomass burning emissions from South America and southern Africa with sporadically strong contributions from Indonesia, the size and strength of the southern hemispheric plume have considerable interannual variations, with monthly mean maxima at, for example, 14 km between 400 and more than 700 pptv. Within 1–2 months after appearance of the plume, a considerable portion of the enhanced HCN is transported southward to as far as Antarctic latitudes. The fundamental period of HCN variability in the northern upper troposphere is also an annual cycle with varying amplitude, which in the tropics peaks in May after and during the biomass burning seasons in northern tropical Africa and southern Asia, and in the subtropics peaks in July due to trapping of pollutants in the Asian monsoon anticyclone (AMA). However, caused by extensive biomass burning in Indonesia and by northward transport of part of the southern hemispheric plume, northern HCN maxima also occur around October/November in several years, which leads to semi-annual cycles. There is also a temporal shift between enhanced HCN in northern low and mid- to high latitudes, indicating northward transport of pollutants. Due to additional biomass burning at mid- and high latitudes, this meridional transport pattern is not as clear as in the Southern Hemisphere. Upper tropospheric HCN volume mixing ratios (VMRs) above the tropical oceans decrease to below 200 pptv, presumably caused by ocean uptake, especially during boreal winter and spring. The tropical stratospheric tape recorder signal with an apparently biennial period, which was detected in MLS and ACE-FTS data from mid-2004 to mid-2007, is corroborated by MIPAS HCN data. The tape recorder signal in the whole MIPAS data set exhibits periodicities of 2 and 4 years, which are generated by interannual variations in biomass burning. The positive anomalies of the years 2003, 2007 and 2011 are caused by succession of strongly enhanced HCN from southern hemispheric and Indonesian biomass burning in boreal autumn and of elevated HCN from northern tropical Africa and the AMA in subsequent spring and summer. The anomaly of 2005 seems to be due to springtime emissions from tropical Africa followed by release from the summertime AMA. The vertical transport time of the anomalies is 1 month or less between 14 and 17 km in the upper troposphere and 8–11 months between 17 and 25 km in the lower stratosphere.
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Emitted mainly by the oceans, iodine is a halogen compound important for atmospheric chemistry due to its high ozone depletion potential and effect on the oxidizing capacity of the atmosphere. Here we present a comprehensive data set of iodine oxide (IO) measurements in the open marine boundary layer (MBL) made during the Malaspina 2010 circumnavigation. Results show IO mixing ratios ranging from 0.4 to 1 pmol mol<sup>−1</sup> (30% uncertainty) and, complemented with additional field campaigns, this data set confirms through observations the ubiquitous presence of reactive iodine chemistry in the global marine environment. We use a global model with organic (CH<sub>3</sub>I, CH<sub>2</sub>ICl, CH<sub>2</sub>I<sub>2</sub> and CH<sub>2</sub>IBr) and inorganic (HOI and I<sub>2</sub>) iodine ocean emissions to investigate the contribution of the different iodine source gases to the budget of IO in the global MBL. In agreement with previous estimates, our results indicate that, globally averaged, the abiotic precursors contribute about 75 % to the IO budget. However, this work reveals a strong geographical pattern in the contribution of organic vs. inorganic precursors to reactive iodine in the global MBL.
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Dust storms are considered to be a natural hazard over the Arabian Peninsula, since they occur all year round with maximum intensity and frequency in Spring and Summer. The Regional Climate Model version 4 (RegCM4) has been used to study the climatology of atmospheric dust over the Arabian Peninsula from 1999 to 2012. This relatively long simulation period samples the meteorological conditions that determine the climatology of mineral dust aerosols over the Arabian Peninsula. The modeled Aerosol Optical Depth (AOD) has been compared against ground-based observations of three Aerosol Robotic Network (AERONET) stations that are distributed over the Arabian Peninsula and daily space based observations from the Multi-angle Imaging SpectroRadiometer (MISR), the Moderate resolution Imaging SpectroRadimeter (MODIS) and Ozone Monitoring Instrument (OMI). The large scale atmospheric circulation and the land surface response that lead to dust uplifting have been analyzed. While the modeled AOD shows that the dust season extends from March to August with two pronounced maxima, one over the northern Arabian Peninsula in March with AOD equal to 0.4 and one over the southern Arabian Peninsula in July with AOD equal to 0.7, the observations show that the dust season extends from April to August with two pronounced maxima, one over the northern Arabian Peninsula in April with AOD equal to 0.5 and one over the southern Arabian Peninsula in July with AOD equal to 0.5. In spring a high pressure dominates the Arabian Peninsula and is responsible for advecting dust from southern and western part of the Arabian Peninsula to northern and eastern part of the Peninsula. Also, fast developed cyclones in northern Arabian Peninsula are responsible for producing strong dust storms over Iraq and Kuwait. However, in summer the main driver of the surface dust emission is the strong northerly wind ("Shamal") that transport dust from the northern Arabian Peninsula toward south parallel to the Arabian Gulf. The AERONET shortwave Top of Atmosphere Radiative Forcing (TOARF) and at the Bottom of Atmosphere Radiative Forcing (BOARF) have been analyzed and compared with the modeled direct radiative forcing of mineral dust aerosol. The annual modeled TOARF and BOARF are −3.3 and −12 W m<sup>−2</sup>, respectively. However, the annual observed TOARF and BOARF are significantly different at −10 and −52 W m<sup>−2</sup>, respectively. The analysis of observed and modeled TOARF agrees with previous studies in highlighting the need for more accurate specification of surface albedo over the region. Due to the high surface albedo of the central Arabian Peninsula, mineral dust aerosols tend to warm the atmosphere in summer (June–August).
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The impacts of representing cloud microphysical processes in a stochastic subcolumn framework are investigated, with emphasis on estimating the aerosol indirect effect. It is shown that subgrid treatment of cloud activation and autoconversion of cloud water to rain reduce the impact of anthropogenic aerosols on cloud properties and thus reduce the global mean aerosol indirect effect by 19%, from −1.59 to −1.28 W m<sup>−2</sup>. This difference is partly related to differences in the model basic state; in particular, the liquid water path (LWP) is smaller and the shortwave cloud radiative forcing weaker when autoconversion is computed separately for each subcolumn. However, when the model is retuned so that the differences in the basic state LWP and radiation balance are largely eliminated, the global-mean aerosol indirect effect is still 14% smaller (i.e. −1.37 W m<sup>−2</sup>) than for the model version without subgrid treatment of cloud activation and autoconversion. The results show the importance of considering subgrid variability in the treatment of autoconversion. Representation of several processes in a self-consistent subgrid framework is emphasized. This paper provides evidence that omitting subgrid variability in cloud microphysics contributes to the apparently chronic overestimation of the aerosol indirect effect by climate models, as compared to satellite-based estimates.
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This study reports the concentrations and potential sources of speciated atmospheric mercury at the Shangri-La Atmosphere Watch Regional Station (SAWRS), a pristine high-altitude site (3580 m a.s.l.) in Tibetan Plateau, China. Total gaseous mercury (TGM, defined as the sum of gaseous elemental mercury, GEM, and gaseous oxidized mercury, GOM), GOM and particulate-bound mercury (PBM) were monitored from November 2009 to November 2010 to investigate the characteristics and potential influence of the Indian summer monsoon (ISM) and the Westerlies on atmospheric transport of mercury. The mean concentrations (± standard deviation) of TGM, PBM and GOM were 2.55 ± 0.73 ng m<sup>−3</sup>, 38.82 ± 31.26 pg m<sup>−3</sup> and 8.22 ± 7.90 pg m<sup>−3</sup>, respectively. A notable seasonal pattern of TGM concentrations was observed with higher concentrations at the beginning and the end of the ISM season. High TGM concentrations (> 2.5 ng m<sup>−3</sup>) were associated with the transport of dry air that carried regional anthropogenic emissions from both Chinese domestic and foreign (e.g., Myanmar, Bay of Bengal, and northern India) sources based on analysis of HYSPLIT4 back trajectories. Somewhat lower PBM and GOM levels during the ISM period were attributed to the enhanced wet scavenging. The high GOM and PBM were likely caused by local photo-chemical transformation under low RH and the domestic biofuel burning in cold seasons.
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Reliable quantification of air–biosphere exchange flux of elemental mercury vapor (Hg<sup>0</sup>) is crucial for understanding the global biogeochemical cycle of mercury. However, there has not been a standard analytical protocol for flux quantification, and little attention has been devoted to characterize the temporal variability and comparability of fluxes measured by different methods. In this study, we deployed a collocated set of micrometeorological (MM) and dynamic flux chamber (DFC) measurement systems to quantify Hg<sup>0</sup> flux over bare soil and low standing crop in an agricultural field. The techniques include relaxed eddy accumulation (REA), modified Bowen ratio (MBR), aerodynamic gradient (AGM) as well as dynamic flux chambers of traditional (TDFC) and novel (NDFC) designs. The five systems and their measured fluxes were cross-examined with respect to magnitude, temporal trend and correlation with environmental variables. <br><br> Fluxes measured by the MM and DFC methods showed distinct temporal trends. The former exhibited a highly dynamic temporal variability while the latter had much more gradual temporal features. The diurnal characteristics reflected the difference in the fundamental processes driving the measurements. The correlations between NDFC and TDFC fluxes and between MBR and AGM fluxes were significant (<i>R</i>>0.8, <i>p</i><0.05), but the correlation between DFC and MM fluxes were from weak to moderate (<i>R</i>=0.1–0.5). Statistical analysis indicated that the median of turbulent fluxes estimated by the three independent MM techniques were not significantly different. Cumulative flux measured by TDFC is considerably lower (42% of AGM and 31% of MBR fluxes) while those measured by NDFC, AGM and MBR were similar (<10% difference). This suggests that incorporating an atmospheric turbulence property such as friction velocity for correcting the DFC-measured flux effectively bridged the gap between the Hg<sup>0</sup> fluxes measured by enclosure and MM techniques. Cumulated flux measured by REA was ~60% higher than the gradient-based fluxes. Environmental factors have different degrees of impacts on the fluxes observed by different techniques, possibly caused by the underlying assumptions specific to each individual method. Recommendations regarding the application of flux quantification methods were made based on the data obtained in this study.
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The environmental impacts of atmospheric particles are highlighted in remote areas where visibility and ecosystem health can be degraded by even relatively low particle concentrations. Submicron particle size, composition, and source apportionment were explored at Rocky Mountain National Park using a High-Resolution Time-of-Flight Aerosol Mass Spectrometer. This summer campaign found low average, but variable, particulate mass (PM) concentrations (max = 93.1 μg m<sup>−3</sup>, avg. = 5.13 ± 2.72 μg m<sup>−3</sup>) of which 75.2 ± 11.1% is organic. Low-volatility oxidized organic aerosol (LV-OOA, 39.3% of PM<sub>1</sub> on average) identified using Positive Matrix Factorization appears to be mixed with ammonium sulfate (3.9% and 16.6% of mass, respectively), while semi-volatile OOA (27.6%) is correlated with ammonium nitrate (nitrate: 4.3%); concentrations of these mixtures are enhanced with upslope (SE) surface winds from the densely populated Front Range area, indicating the importance of transport. A local biomass burning organic aerosol (BBOA, 8.4%) source is suggested by mass spectral cellulose combustion markers (<i>m/z</i> 60 and 73) limited to brief, high-concentration, polydisperse events (suggesting fresh combustion), a diurnal maximum at 22:00 local standard time when campfires were set at adjacent summer camps, and association with surface winds consistent with local campfire locations. The particle characteristics determined here represent typical summertime conditions at the Rocky Mountain site based on comparison to ~10 years of meteorological, particle composition, and fire data.
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The Regional Carbon Balance in Amazonia (BARCA) campaign provided the first Amazon Basin-wide aircraft measurements of ozone (O<sub>3</sub>) during both the dry-to-wet (November and December 2008) and wet-to-dry (May 2009) transition seasons. Extremely low background values (< 20 ppb) were observed to the west and north of Manaus in both seasons and in all regions during the wet-to-dry transition. On the other hand, elevated O<sub>3</sub> levels (40–60 ppb) were seen during the dry-to-wet transition to the east and south of Manaus, where biomass burning emissions of O<sub>3</sub> precursors were present. Chemistry simulations with the CCATT-BRAMS and WRF-Chem models are within the error bars of the observed O<sub>3</sub> profiles in the boundary layer (0–3 km a.s.l.) in polluted conditions. However, the models overestimate O<sub>3</sub> in the boundary layer in clean conditions, despite lacking the predominant NO source from soil. In addition, O<sub>3</sub> simulated by the models was either within the error bars or lower than BARCA observations in mid-levels (3–5 km a.s.l.), and lower than total tropospheric O<sub>3</sub> retrieved from the OMI/MLS instruments, which is primarily comprised of middle troposphere O<sub>3</sub> and thus reflects long-range transport processes. Therefore, the models do a relatively poor job of representing the free troposphere-boundary layer gradient in O<sub>3</sub> compared with aircraft and satellite observations, which could be due to missing long-range and convective transport of O<sub>3</sub> at mid-levels. Additional simulations with WRF-Chem showed that the model O<sub>3</sub> production is very sensitive to both the O<sub>3</sub> deposition velocities and the NO<sub>x</sub> emissions, which were both about one-half of observed values. These results indicate the necessity of more realistic model representations of emissions, deposition, and convective processes for accurate monitoring and prediction of increases in O<sub>3</sub> production in the Amazon Basin as the regional population grows.
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We examine the parameterized model of Stuart et al. (2013) vis-à-vis a diffusion-based model proposed by us earlier (Anand and Mayya, 2011) to estimate the fraction of aerosol particles surviving coagulation in a dispersing plume. While the Stuart et al. approach is based on the solutions to the coagulation problem in an expanding plume model, the diffusion-based approach solves the diffusion–coagulation equation for a steady-state standing plume to arrive at the survival fraction correlations. We discuss the differences in the functional forms of the survival fraction expressions obtained in the two approaches and compare the results for the case studies presented in Stuart et al. (2013) involving different particle emission rates and atmospheric stability categories. There appears to be a better agreement between the two models at higher survival fractions as compared to lower survival fractions; on the whole, the two models agree with each other within a difference of 10%. The diffusion-based expression involves a single exponent fit to a theoretically generated similarity variable combining the parameters of the problem with inbuilt exponents and hence avoids the multi-exponent parameterization exercise. It also possesses a wider range of applicability in respect of the source and atmospheric parameters as compared to that based on parameterization. However, in the diffusion model, the choice of a representative value for the coagulation coefficient is more prescriptive than rigorous, which has been addressed in a more satisfactory manner by the parameterization method. The present comparative exercise, although limited in scope, confirms the importance of aerosol microphysical processes envisaged by Stuart et al. for cloud brightening applications. In a larger context, it seems to suggest that either of the two forms of expressions might be suitable for incorporation into global-/regional-scale air pollution models for predicting the contribution of localized sources to the particle number loading in the atmosphere.
