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An investigation of atmospheric trace metals was conducted in Oxford, UK, a small city ∼60 miles northwest of London, in 2007 and 2008. Concentrations of Sr, Mo, Cd, Pb, V, Cr, Mn, Fe, Co, Ni, Cu and Zn in aerosol were measured in bulk and size segregated samples. In addition, total gaseous mercury (TGM) concentrations were monitored semi-continuously by cold vapour-atomic fluorescence spectroscopy. Metal concentrations in Oxford were intermediate between previously reported levels of UK rural and urban areas for most metals studied and levels of Cd, Ni and Pb were within European guidelines. Metal concentrations appeared to be influenced by higher traffic volume on a timescale of hours. The influence of traffic on the aerosols was also suggested by the observation of carbonaceous particles via scanning electron microscopy (SEM). Air mass back trajectories suggest air masses arriving in Oxford from London and mainland Europe contained the highest metal concentrations. Aerosol samples collected over Bonfire Weekend, a period of intense firework use and lighting of bonfires in the UK, showed metal concentrations 6-46 times higher than at other times. Strontium, a tracer of firework release, was present at higher concentrations and showed a change in its size distribution from the coarse to fine mode over Bonfire Weekend. The presence of an abundance of spherical Sr particles was also confirmed in SEM images. The average TGM concentration in Oxford was 3.17 ng m-3 (st. dev. 1.59) with values recorded between 1.32 and 23.2 ng m-3. This is a higher average value than reported from nearby rural locations, although during periods when air was arriving from the west, similar concentrations to these rural areas were seen in Oxford. Comparison to meteorological data suggests that TGM in Oxford's air is highest when wind is arriving from the east/southeast. This may be due to emissions from London/mainland Europe with a possible contribution from emissions from a local crematorium situated 4 miles east of the sampling site. A diurnal pattern was also observed in the TGM data with a minimum concentration during the day when mercury may have been diluted by thermal mixing of the atmospheric boundary layer. Additionally, this diurnal pattern may reflect variations in a local source of TGM. © 2010 Elsevier Ltd. All rights reserved.

There is an urgent need to better constrain the global rates of mercury degassing from natural sources, including active volcanoes. Hitherto, estimates of volcanic fluxes have been limited by the poorly determined speciation of Hg in volcanic emissions. Here, we present a systematic characterisation of mercury partitioning between gaseous (Hg(g)) and particulate (Hg(p)) forms in the volcanic plume of Mount Etna, the largest open-vent passively degassing volcano on Earth. We demonstrate that mercury transport is predominantly in the gas phase, with a mean Hg(p)/Hg(g) ratio of ∼0.01 by mass. We also present the first simultaneous measurement of divalent gaseous mercury ( Hg ( g ) II ) and total gaseous mercury (Hg(g)) in a volcanic plume, which suggests that Hg ( g ) 0 is the prevalent form of mercury in this context. These data are supported by the results of model simulations, carried out with HSC thermodynamic software. Based on a mean “bulk plume” Hg/SO2 mass ratio of 8.7×10−6, and a contemporaneous volcanic SO2 flux of 0.8 Mt yr−1, we estimate an Hg emission rate from Mt. Etna during passive degassing of 5.4 t yr−1 (range, 1.1–10 t yr−1). This corresponds to ∼0.6% of global volcanic Hg emissions, and about 5% of Hg released from industrial activities in the Mediterranean area.

We report here the first observations of NO2 emission from Mt. Erebus, a volcano with an active lava lake located on Ross Island, Antarctica. Erebus generates a persistent plume, which is entrained at an altitude of about 4 km above sea level. Its NO2 flux, measured by scattered light ultraviolet spectroscopy in December 2003, was equivalent to ∼0.6 Gg (N) yr-1. The total reactive nitrogen supply may be significantly higher than this since other NOy species are likely to have been present in the plume. We believe the NO2 is generated by thermal fixation of atmospheric nitrogen at the hot lava surface, forming NO, which then reacts rapidly with oxidants including ozone to yield NO2. Erebus volcano has displayed lava lake activity for many decades and may, therefore, play a significant long-term role in Antarctic tropospheric chemistry, and represent an important source of nitrogen deposited to the ice surface. © 2005 Elsevier Ltd. All rights reserved.

Filter packs have been used to collect sulphur and oxygen from air for isotope analysis from many areas of the world. Here we discuss their use to determine the sulphur isotope systematics of SO2 and the sulphur and oxygen systematics of sulphate particles from volcanic vents. Our field data suggest that fractionation of sulphur isotopes occurs during the collection of SO2 from concentrated volcanic gas plumes on alkali-impregnated filter papers. The collection of volcanogenic HCl on the same filters may play a role in this fractionation. Comparison with previous studies, which sampled areas of cleaner atmosphere, suggests that isotopic fractionation only becomes significant where elevated filter loadings occur (e.g., when sampling gas streams with SO2 concentrations greater than ∼1 μmol m-3), although this requires further investigation. Previous studies also suggest that for volcanic sulphate particle samples collected at the same time, oxygen isotopes are fractionated while sulphur isotopes are not. Minimising the filter loading reduces these effects, but there is a trade-off with the amount of SO2 or SO42 - required for isotopic measurements. Despite the convenience of the filter pack technique these fractionation effects limit the use of filter packs for determining δ34S for SO2 in volcanic gases and δ18O and δ17O for the sulphate in volcanic particles, and they will certainly not be useful for determining small variations in the source isotopic signature of the sulphur in the SO2 or the oxygen in the SO42 - being measured. This highlights the importance of collecting SO2 quantitatively for isotopic analysis. These effects may also have implications if using similar methods to collect SO2 in other environments, especially where concentrations are high. © 2008 Elsevier Ltd. All rights reserved.