Volcanoes as emission sources of atmospheric mercury in the Mediterranean basin

Emissions from volcanoes, fumaroles and solfataras as well as contributions from widespread geological anomalies could represent an important source of mercury released to the atmosphere in the Mediterranean basin. Volcanoes located in this area (Etna, Stromboli and Vulcano) are the most active in Europe; therefore, it is extremely important to know their mercury contributions to the regional atmospheric budget. Two main methods are used for the evaluation of volcanic mercury flux: a direct determination of the flux (by measuring in the plume) and an indirect one derived from the determination of the Hg/SO2 (or Hg/S) ratio value, as SO2 emissions are constantly monitored by volcanologists. An attempt to estimate mercury flux from the Vulcano volcano and to establish the Hg/S ratio value has been made along three field campaigns carried out in October 1998, in February and May 1999 sampling several fumaroles. Traditional sampling methods were used to collect both total Hg and S. The average Hg/S ratio value resulted to be 1.2 x 10(-7). From the Hg/S value we derived the Hg/SO2 value, and by assuming that all the volcanoes located in this area have the same Hg/SO2 ratio, mercury emissions from Vulcano and Stromboli were estimated to be in the range 1.3-5.5 kg/year and 7.3-76.6 kg/year respectively, while for Etna mercury flux ranged from 61.8 to 536.5 kg/year. Data reported in literature appear to be overestimated (Fitzgerald WF. Mercury emission from volcanos. In: 4th International conference on mercury as a global pollutant, August 4-8 1996, Hamburg, Germany), volcanic mercury emission does not constitute the main natural source of the metal.

Temporal trends in gaseous mercury evasion from the Mediterranean seawaters.

Mercury evasion from seawaters is considered to be one of the main natural sources of mercury released to the atmosphere. The temporal evolution of this mechanism is related to biotic and abiotic processes that produce mercury in its elemental form and as DGM. The efficiency of these processes depends upon the intensity of the solar radiation, the ambient temperature of the air parcel above the seawater, and the water temperature. In the Mediterranean region, the magnitude of these mechanisms are particularly significant, due to favorable climate conditions and to the presence of large cinnabar deposits that cross the whole region; all these synergic factors yield significant evasional fluxes of mercury from the surface water during most of the annual period. In this work, mercury fluxes were measured by using a floating flux chamber connected to an atomic absorption analyzer. Photosynthetic active radiation (PAR) and UV components of the solar radiation were measured using the same system adopted in the EC 'ELDONet project'. The measurements of the mercury evasional fluxes were carried out at three sites of the northern Tyrrhenian Sea during 1998. Two sites were located at unpolluted and polluted coastal areas, and the third was an offshore site. The evasional flux showed a typical daily trend, highest at midday when the ambient temperature and solar radiation were at the maximum, and lowest, near to zero, during the night. Besides the day-night behavior, a seasonal trend was also observed, with minimum values during the winter period (0.7-2.0 ng/m2 h) and maximum values during the summer (10-13 ng/m2 h).

Conversion of tyrosine to phenolic derivatives by Taiwan cobra venom.

We have examined the ability of Taiwan cobra (Naja naja atra) venom to transform in vitro the amino acid tyrosine to phenolic oxidation products via 4-hydroxyphenylpyruvate. This amino acid can be released from neuropeptide substrates by oligopeptidases present in the venom. Using a variety of analytical techniques to probe a complicated series of reactions, we confirm that the L-amino acid oxidase present in the venom initially releases the keto form of 4-hydroxyphenylpyruvic acid and hydrogen peroxide after reacting with the tyrosine. Thereafter, there is evidence that a tautomerase in the venom promotes a partial conversion of the keto-form 4-hydroxyphenylpyruvic acid into an enol form. The enol is oxidised primarily to 4-hydroxybenzaldehyde and 4-hydroxyphenol (hydroquinone). The keto form is oxidised through to 4-hydroxyphenylacetic acid by the hydrogen peroxide co-released by the L-amino acid oxidase. The venom promotes both these spontaneous oxidation routes and also generates traces of other phenolics, some of which are as yet unidentified. We propose that reactions between the precursors of the major oxidation products may be responsible for generating unusual short-lived phenolics, possibly giving rise to special bioactivities that are relevant to venom action.