The authors evaluated continuous high-resolution gaseous elemental mercury (GEM) data from the Cape Point Global Atmosphere Watch (CPT GAW) station with different statistical analysis techniques. GEM ...data were evaluated by cluster analysis and the results indicated that two clusters, separated at 0.904 ng m-3, existed. The air mass history for the two-cluster solution was investigated by means of back-trajectory analysis. The air mass back-trajectory net result showed lower GEM concentrations originating from the sparsely populated semi-arid interior of South Africa and the marine environment, whereas higher GEM concentrations originated predominately along the coast of South Africa that most likely coincide with trade routes and industrial activities in urban areas along the coast. Considering the net result from the air mass back-trajectories, it is evident that not all low GEM concentrations are from marine origin, and similarly, not all high GEM concentrations have a terrestrial origin. Equations were developed by means of multi-linear regression (MLR) analysis that allowed for the estimation and/or prediction of atmospheric GEM concentrations from other atmospheric parameters measured at the CPT GAW station. These equations also provided some insight into the relation and interaction of GEM with other atmospheric parameters. Both measured and MLR calculated data confirm a decline in GEM concentrations at CPT GAW over the period evaluated.
Mercury emissions in South Africa have so far been estimated only by a bottom-up approach from activities and emission factors for different processes. In this paper we derive GEM/CO (GEM being ...gaseous elemental mercury, Hg0), GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios from plumes observed during long-term monitoring of these species at Cape Point between March 2007 and December 2009. The average observed GEM/CO, GEM/CO2, GEM/CH4, CO/CO2, CH4/CO2, and CH4/CO emission ratios were 2.40 ± 2.65 pg m−3 ppb−1 (n = 47), 62.7 ± 80.2 pg m−3 ppm−1 (n = 44), 3.61 ± 4.66 pg m−3 ppb−1 (n = 46), 35.6 ± 25.4 ppb ppm−1 (n = 52), 20.2 ± 15.5 ppb ppm−1 (n = 48), and 0.876 ± 1.106 ppb ppb−1 (n = 42), respectively. The observed CO/CO2, CH4/CO2, and CH4/CO emission ratios agree within the combined uncertainties of the observations and emissions with the ratios calculated from EDGAR (version 4.2) CO2, CO, and CH4 inventories for South Africa and southern Africa (South Africa, Lesotho, Swaziland, Namibia, Botswana, Zimbabwe, and Mozambique) in 2007 and 2008 (inventories for 2009 are not available yet). Total elemental mercury emission of 13.1, 15.2, and 16.1 t Hg yr−1 are estimated independently using the GEM/CO, GEM/CO2, and GEM/CH4 emission ratios and the annual mean CO, CO2, and CH4 emissions, respectively, of South Africa in 2007 and 2008. The average of these independent estimates of 14.8 t GEM yr−1 is much less than the total emission of 257 t Hg yr−1 shown by older inventories which are now considered to be wrong. Considering the uncertainties of our emission estimate, of the emission inventories, and the fact that emission of GEM represents 50–78 % of all mercury emissions, our estimate is comparable to the currently cited GEM emissions in 2004 and somewhat smaller than emissions in 2006. A further increase of mercury emissions due to increasing electricity consumption will lead to a more pronounced difference. A quantitative assessment of the difference and its significance, however, will require emission inventories for the years of observations (2007–2009) as well as better data on the speciation of the total mercury emissions in South Africa.
The ash cloud of the Eyjafjallajökull (also referred to as: Eyjafjalla (e.g. Schumann et al., 2011), Eyjafjöll or Eyjafjoll (e.g. Ansmann et al., 2010)) volcano on Iceland caused closure of large ...parts of European airspace in April and May 2010. For the validation and improvement of the European volcanic ash forecast models several research flights were performed. Also the CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) flying laboratory, which routinely measures at cruise altitude (approximate11 km) performed three dedicated measurements flights through sections of the ash plume. Although the focus of these flights was on the detection and quantification of the volcanic ash, we report here on sulphur dioxide (SO2 ) and bromine monoxide (BrO) measurements with the CARIBIC DOAS (Differential Optical Absorption Spectroscopy) instrument during the second of these special flights on 16 May 2010. As the BrO and the SO2 observations coincide, we assume the BrO to have been formed inside the volcanic plume. Average SO2 and BrO mixing ratios of approximate40 ppb and approximate5 ppt respectively are retrieved inside the plume. The BrO to SO2 ratio retrieved from the CARIBIC observation is approximate1.3×10-4 . Both SO2 and BrO observations agree well with simultaneous satellite (GOME-2) observations. SO2 column densities retrieved from satellite observations are often used as an indicator for volcanic ash. As the CARIBIC O4 column densities changed rapidly during the plume observation, we conclude that the aerosol and the SO2 plume are collocated. For SO2 some additional information on the local distribution can be derived from a comparison of forward and back scan GOME-2 data. More details on the local plume size and position are retrieved by combining CARIBIC and GOME-2 data.
Total gaseous mercury (TGM) has been measured at the WMO Global Atmosphere Watch (GAW) station at Cape Point, South Africa, since September 1995, representing the only long term TGM measurement in ...the Southern Hemisphere (SH) so far. Annual medians suggest a small but significant decrease of TGM concentrations from 1.29 ng m−3 in 1996 to 1.19 ng m−3 in 2004. Background TGM concentrations at Cape Point varied seasonally, with a summer maximum and a winter minimum. Comparison with the seasonal variation of CO concentrations in both hemispheres calls into question the influence of mercury sink by the Hg0 + OH reaction. If confirmed at other sites in the SH, the observed TGM seasonal variation may pose an important constraint on the global models of atmospheric mercury.
In this study, the concentrations of total gaseous mercury in baseline air masses arriving at Mace Head, Ireland after having traversed the thousands of kilometres uninterrupted fetch of the North ...Atlantic Ocean, have been used for the assessment of possible trends in the atmospheric mercury background concentration over a 14-year period (i.e., 1996–2009), a statistically significant negative (downwards) trend of −0.028 ± 0.01 ng m
−3 yr
−1, representing a trend of 1.6–2.0% per year, has been detected in the total gaseous mercury levels in these baseline air masses. These findings are set in the context of the available literature studies of atmospheric Hg trends.
► Our data set is the longest existing time series for Hg in temperate background air. ► More than 40 000 concentration measurements could be attributed to NH background air. ► We find a downward trend of 1.6–2.0%/yr over the 14 years measurement period. ► This decline is large in comparison to that seen in other trace gases. ► This decline contradicts current global emission inventories for mercury.
Hexachlorocyclohexanes (HCHs) are ubiquitous organic pollutants derived from pesticide application. They are subject to long-range transport, persistent in the environment, and capable of ...accumulation in biota. Shipboard measurements of HCH isomers (α-, γ- and β-HCH) in surface seawater and boundary layer atmospheric samples were conducted in the Atlantic and the Southern Ocean in October to December of 2008. ΣHCHs concentrations (the sum of α-, γ- and β-HCH) in the lower atmosphere ranged from 12 to 37 pg m−3 (mean: 27 ± 11 pg m−3) in the Northern Hemisphere (NH), and from 1.5 to 4.0 pg m−3 (mean: 2.8 ± 1.1 pg m−3) in the Southern Hemisphere (SH), respectively. Water concentrations were: α-HCH 0.33–47 pg l−1, γ-HCH 0.02–33 pg l−1 and β-HCH 0.11–9.5 pg l−1. Dissolved HCH concentrations decreased from the North Atlantic to the Southern Ocean, indicating historical use of HCHs in the NH. Spatial distribution showed increasing concentrations from the equator towards North and South latitudes illustrating the concept of cold trapping in high latitudes and less interhemispheric mixing process. In comparison to concentrations measured in 1987–1999/2000, gaseous HCHs were slightly lower, while dissolved HCHs decreased by factor of 2–3 orders of magnitude. Air-water exchange gradients suggested net deposition for α-HCH (mean: 3800 pg m−2 day−1) and γ-HCH (mean: 2000 pg m−2 day−1), whereas β-HCH varied between equilibrium (volatilization: <0–12 pg m−2 day−1) and net deposition (range: 6–690 pg m−2 day−1). Climate change may significantly accelerate the release of "old" HCHs from continental storage (e.g. soil, vegetation and high mountains) and drive long-range transport from sources to deposition in the open oceans. Biological productivities may interfere with the air-water exchange process as well. Consequently, further investigation is necessary to elucidate the long term trends and the biogeochemical turnover of HCHs in the oceanic environment.
Plumes of biomass burning effluents were observed during CARIBIC flights between São Paulo and Santiago de Chile on August 31 and October 5, 2005, as well as during the last part of the flight from ...Frankfurt to São Paulo on October 4, 2005. Total gaseous mercury (TGM) correlated with CO on August 31 and October 4 yielding a TGM/CO emission ratio of (1.2 ± 0.2) × 10−7 and (2.4 ± 1.0) × 10−7 mol/mol, respectively. No significant TGM/CO correlation was observed on October 5 probably because of variable background concentrations of both gases. The TGM/CO emission ratios observed here over South America fall within the rather narrow range of (0.67–2.4) × 10−7 mol/mol reported hitherto for sites geographically as different as South Africa, Canada, and the U.S.A. A total average emission of 437 Tg CO/yr from biomass burning over the years 1996–2000 implies an average TGM emission of 210–750 t/yr from biomass burning, representing 3–11% of all mercury emissions. TGM emissions from biomass burning are likely to be larger than anthropogenic emissions in the southern hemisphere during the burning season in August–October.
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