Atmosphere2014, 5(3), 622-634; doi:10.3390/atmos5030622 - published 22 August 2014 Show/Hide Abstract
Abstract: A diel (24-h) cycle with daytime atmospheric concentrations higher than nighttime concentrations by a factor of 1.5–3 was observed for several low molecular weight polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons (PAHs) in remote areas of the tropical South Atlantic during a cruise in October–November 2005. In contrast, high molecular weight PCBs and PAHs did not display diurnal variability. A model which has successfully explained diel variability of persistent organic pollutants (POPs) over land could not reproduce the observed diel cycle by considering variability in temperature, atmospheric OH radical concentrations, atmospheric boundary layer height and wind speed as causal factors. We used the model to conduct two bounding scenarios to explore the possibility that phytoplankton biomass turn-over in the surface ocean drives the observed variability in air concentrations. The model could only qualitatively reproduce the field observations of diel variability for low chlorinated PCB congeners when the ocean acts as a source of pollutants to the atmosphere, and when variability in biomass drives variability in the capacity of the surface ocean.
Atmosphere2014, 5(3), 597-621; doi:10.3390/atmos5030597 - published 22 August 2014 Show/Hide Abstract
Abstract: We present here a simple retrieval of the areal-averaged spectral surface albedo using only ground-based measurements of atmospheric transmission under fully overcast conditions. Our retrieval is based on a one-line equation. The feasibility of our retrieval for routine determinations of albedo is demonstrated for different landscapes with various degrees of heterogeneity using three sets of measurements: (1) spectral atmospheric transmission from the Multi-Filter Rotating Shadowband Radiometer (MFRSR) at five wavelengths (415, 500, 615, 673, and 870 nm); (2) tower-based measurements of local surface albedo at the same wavelengths; and (3) areal-averaged surface albedo at four wavelengths (470, 560, 670 and 860 nm) from collocated and coincident Moderate Resolution Imaging Spectroradiometer (MODIS) observations. These integrated datasets cover both temporally long (2008–2013) and short (April–May 2010) periods at the Atmospheric Radiation Measurement (ARM) Southern Great Plains site and the National Oceanic and Atmospheric Administration (NOAA) Table Mountain site, respectively. The calculated root mean square error (RMSE), defined here as the root mean squared difference between the MODIS-derived surface albedo and the retrieved areal-averaged albedo, is quite small (RMSE ≤ 0.015) and comparable with that obtained previously by other investigators for the shortwave broadband albedo. Good agreement between tower-based measurements of daily-averaged surface albedo for completely overcast and non-overcast conditions is also demonstrated.
Atmosphere2014, 5(3), 575-596; doi:10.3390/atmos5030575 - published 13 August 2014 Show/Hide Abstract
Abstract: Programmable Thermal Dissociation (PTD) has been used to investigate the chemical speciation of Reactive Gaseous Mercury (RGM, Hg2+). RGM was collected on denuders and analyzed using PTD. The technique was tested in a field campaign at a coal-fired power plant in Pensacola, Florida. Stack gas samples were collected from ducts located after the electrostatic precipitator and prior to entering the stack. An airship was used to sample from the stack plume, downwind of the stack exit. The PTD profiles from these samples were compared with PTD profiles of HgCl2. Comparison of stack and in-plume samples suggest that the chemical speciation are the same and that it is possible to track a specific chemical form of RGM from the stack and follow its evolution in the stack plume. Comparison of the measured plume RGM with the amount calculated from in-stack measurements and the measured plume dilution suggest that the stack and plume RGM concentrations are consistent with dilution. The PTD profiles of the stack and plume samples are consistent with HgCl2 being the chemical form of the sampled RGM. Comparison with literature PTD profiles of reference mercury compounds suggests no other likely candidates for the speciation of RGM.
Atmosphere2014, 5(3), 557-574; doi:10.3390/atmos5030557 - published 13 August 2014 Show/Hide Abstract
Abstract: Atmospheric transport and in situ oxidation are important factors influencing mercury concentrations at the surface and wet and dry deposition rates. Contributions of both natural and anthropogenic processes can significantly impact burdens of mercury on local, regional and global scales. To address these key issues in atmospheric mercury research, airborne measurements of mercury speciation and ancillary parameters were conducted over a region near Tullahoma, Tennessee, USA, from August 2012 to June 2013. Here, for the first time, we present vertical profiles of Hg speciation from aircraft for an annual cycle over the same location. These airborne measurements included gaseous elemental mercury (GEM), gaseous oxidized mercury (GOM) and particulate bound mercury (PBM), as well as ozone (O3), sulfur dioxide (SO2), condensation nuclei (CN) and meteorological parameters. The flights, each lasting ~3 h, were conducted typically one week out of each month to characterize seasonality in mercury concentrations. Data obtained from 0 to 6 km altitudes show that GEM exhibited a relatively constant vertical profile for all seasons with an average concentration of 1.38 ± 0.17 ng∙m−3. A pronounced seasonality of GOM was observed, with the highest GOM concentrations up to 120 pg∙m−3 in the summer flights and lowest (0–20 pg∙m−3) in the winter flights. Vertical profiles of GOM show the maximum levels at altitudes between 2 and 4 km. Limited PBM measurements exhibit similar levels to GOM at all altitudes. HYSPLIT back trajectories showed that the trajectories for elevated GOM (>70 pg∙m−3) or PBM concentrations (>30 pg∙m−3) were largely associated with air masses coming from west/northwest, while events with low GOM (<20 pg∙m−3) or PBM concentrations (<5 pg∙m−3) were generally associated with winds from a wider range of wind directions. This is the first set of speciated mercury vertical profiles collected in a single location over the course of a year. Even though there are current concerns that the KCl denuders used in this study may under-collect GOM, especially in the presence of elevated ozone, the collected data in this region shows the strong seasonality of oxidized mercury concentrations throughout the low to middle free troposphere.
Atmosphere2014, 5(3), 536-556; doi:10.3390/atmos5030536 - published 12 August 2014 Show/Hide Abstract
Abstract: Atmospheric Total Gaseous Mercury (TGM) concentrations were monitored in Windsor, Ontario, Canada, during 2007 to 2011, to investigate the temporal variability of TGM. Over five years, the average concentration was 2.0 ± 1.3 ng/m3. A gradual decrease in annual TGM concentrations from 2.0 ng/m3 in year 2007 to 1.7 ng/m3 in 2009 was observed. The seasonal means show the highest TGM concentrations during the summer months (2.4 ± 2.0 ng/m3), followed by winter (1.9 ± 1.4 ng/m3), fall (1.8 ± 0.81 ng/m3), and spring (1.7 ± 0.73 ng/m3). Diurnal patterns in summer, fall, and winter were similar. A different diurnal pattern was observed in spring with an early depletion in the morning. The TGM concentrations were lower on weekends (1.8 ± 0.77 ng/m3) than on weekdays (2.0 ± 1.5 ng/m3), suggesting 10% of TGM in Windsor was attributable to emissions from industrial sectors in the region. Directional TGM concentrations also indicated southwesterly air masses were TGM enriched due to emissions from coal-fired power plants and industrial facilities. Correlation and principal component analysis identified that combustion of fossil fuel, ambient temperature, wind speed, synoptic systems, and O3 concentrations influenced TGM concentrations significantly. Overall, inter-annual, seasonal, day-of-week, and diurnal variability was observed in Windsor. The temporal patterns were affected by anthropogenic and surface emissions, as well as atmospheric mixing and chemistry.
Abstract: Ozone and methane are chemically active climate-forcing agents affected by climate–chemistry interactions in the atmosphere. Key chemical reactions and processes affecting ozone and methane are presented. It is shown that climate-chemistry interactions have a significant impact on the two compounds. Ozone, which is a secondary compound in the atmosphere, produced and broken down mainly in the troposphere and stratosphre through chemical reactions involving atomic oxygen (O), NOx compounds (NO, NO2), CO, hydrogen radicals (OH, HO2), volatile organic compounds (VOC) and chlorine (Cl, ClO) and bromine (Br, BrO). Ozone is broken down through changes in the atmospheric distribution of the afore mentioned compounds. Methane is a primary compound emitted from different sources (wetlands, rice production, livestock, mining, oil and gas production and landfills).Methane is broken down by the hydroxyl radical (OH). OH is significantly affected by methane emissions, defined by the feedback factor, currently estimated to be in the range 1.3 to 1.5, and increasing with increasing methane emission. Ozone and methane changes are affected by NOx emissions. While ozone in general increase with increases in NOx emission, methane is reduced, due to increases in OH. Several processes where current and future changes have implications for climate-chemistry interactions are identified. It is also shown that climatic changes through dynamic processes could have significant impact on the atmospheric chemical distribution of ozone and methane, as we can see through the impact of Quasi Biennial Oscillation (QBO). Modeling studies indicate that increases in ozone could be more pronounced toward the end of this century. Thawing permafrost could lead to important positive feedbacks in the climate system. Large amounts of organic material are stored in the upper layers of the permafrost in the yedoma deposits in Siberia, where 2 to 5% of the deposits could be organic material. During thawing of permafrost, parts of the organic material that is deposited could be converted to methane. Furthermore, methane stored in deposits under shallow waters in the Arctic have the potential to be released in a future warmer climate with enhanced climate impact on methane, ozone and stratospheric water vapor. Studies performed by several groups show that the transport sectors have the potential for significant impacts on climate-chemistry interactions. There are large uncertainties connected to ozone and methane changes from the transport sector, and to methane release and climate impact during permafrost thawing.