Measurements of atmospheric mercury species at a coastal site in the Antarctic and over the south Atlantic Ocean during polar summer.

Mercury and many of its compounds behave exceptionally in the environment because of their volatility, capability for methylation, and subsequent biomagnification in contrast with most of the other heavy metals. Long-range atmospheric transport of elemental mercury, its transformation to more toxic methylmercury compounds, the ability of some to undergo photochemical reactions, and their bioaccumulation in the aquatic food chain have made it a subject of global research activities, even in polar regions. The first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period were carried out at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W) between January 2000 and February 2001. We recently reported that mercury depletion events (MDEs) occur in the Antarctic after polar sunrise, as was previously shown for Arctic sites. These events (MDEs) end suddenly during Antarctic summer. A possible explanation of this phenomenon is presented in this paper, showing that air masses originating from the sea-ice surface were a necessary prerequisite for the observations of depletion of atmospheric mercury at polar spring. Our extensive measurements at Neumayer of atmospheric mercury species during December 2000-February 2001 show that fast oxidation of gaseous elemental mercury leads to variable Hg0 concentrations during Antarctic summer, accompanied by elevated concentrations, up to more than 300 pg/m3, of reactive gaseous mercury. For the first time in the Southern Hemisphere, atmospheric mercury species measurements were also performed onboard of a research vessel, indicating the existence of homogeneous background concentrations over the south Atlantic Ocean. These new findings contain evidence for an enhanced oxidizing potential of the Antarctic atmosphere over the continent that needs to be considered for the interpretation of dynamic transformations of mercury during summertime.

Time series analysis of long-term data sets of atmospheric mercury concentrations.

Different aspects and techniques of time series analysis were used to investigate long-term data sets of atmospheric mercury in the Northern Hemisphere. Two perennial time series from different latitudes with different seasonal behaviour were chosen: first, Mace Head on the west coast of Ireland (53 degrees 20'N, 9 degrees 54'W), representing Northern Hemispherical background conditions in Europe with no indications for so-called atmospheric mercury depletion events (AMDEs); and second, Alert, Canada (82 degrees 28'N, 62 degrees 30'W), showing strong AMDEs during Arctic springtime. Possible trends were extracted and forecasts were performed by using seasonal decomposition procedures, autoregressive integrated moving average (ARIMA) methods and exponential smoothing (ES) techniques. The application of time series analysis to environmental data is shown in respect of atmospheric long-term data sets, and selected advantages are discussed. Both time series have not shown any statistically significant temporal trend in the gaseous elemental mercury (GEM) concentrations since 1995, representing low Northern Hemispherical background concentrations of 1.72+/-0.09 ng m(-3) (Mace Head) and 1.55+/-0.18 ng m(-3) (Alert), respectively. The annual forecasts for the GEM concentrations in 2001 at Alert by two different techniques were in good agreement with the measured concentrations for this year.

Evaluation and applications of a gaseous mercuric chloride source.

In this study, a diffusion-type device for generating gaseous mercuric chloride (HgCl(2)) was systematically evaluated and applied to validate the annular denuder method for sampling gaseous HgCl(2) species in a synthetic gas stream. The results show that it takes at least 48 h for the system to reach a steady-state condition after the diffusion cell reaches the temperature set-point and the carrier gas is activated. The primary Hg species from the source was proven to be HgCl(2). In the temperature range from -5.00 to 11.80 degrees C, the Hg emission rates from the source vary from 1.8 to 14.2 pg min(-1). It is shown that, under the experimental conditions examined, KCl-coated annular quartz denuders designed for ambient reactive gaseous mercury (RGM) collection could quantitatively collect HgCl(2). It is also demonstrated that the impactors used to remove coarse airborne particulate matter could lead to a loss of up to one third of the HgCl(2) in the gas stream.

Analysis of inorganic mercury species associated with airborne particulate matter/aerosols: method development.

This paper describes a method for speciation of Hg associated with airborne particulate matter. This method uses a mini-sampler for sample collection and analysis, thermal desorption for separating Hg species, and inductively coupled plasma mass spectrometry (ICP-MS) for identification and quantification of Hg. Coal fly ash spiked with different Hg compounds (e.g. Hg0, HgCl2, HgO, and HgS) was used for qualitative calibration. A standard reference material with a certified value for Hg concentration was used to evaluate the method. When the temperature of the furnace was programmed at a linear rate of increase of 50 degrees min(-1), different Hg compounds could clearly be separated. Three airborne particulate matter samples were collected in parallel in Toronto, ON, Canada and analyzed using this method. Reproducible results were obtained and Hg0, HgCl2, HgO, and HgS species from these samples were detected.

Antarctic springtime depletion of atmospheric mercury.

Unlike other heavy metals that are inherently associated with atmospheric aerosols, mercury in ambient air exists predominantly in the gaseous elemental form. Because of its prolonged atmospheric residence time, elemental mercury vapor is distributed on a global scale. Recently, Canadian researchers have discovered that total gaseous mercury levels in the lower tropospheric boundary layer in the Canadian Arctic are often significantly depleted during the months after polar sunrise. A possible explanation may involve oxidation of elemental mercury, followed by adsorption and deposition of the oxidized form, leading to an increased input of atmospheric mercury into the Arctic ecosystem. Here we present the first continuous high-time-resolution measurements of total gaseous mercury in the Antarctic covering a 12-month period between January 2000 and January 2001 at the German Antarctic research station Neumayer (70 degrees 39' S, 8 degrees 15' W). We report that mercury depletion events also occur in the Antarctic after polar sunrise and compare our measurements with a data setfrom Alert, Nunavut, Canada. We also present indications that BrO radicals and ozone play a key role in the boundary-layer chemistry during springtime mercury depletion events in the Antarctic troposphere.