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- Acke, Filip, et al.
(författare)
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Study of the reduction and reoxidation of a CaO surface
- 1997
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Ingår i: J Phys Chem B. - 1520-5207 .- 1520-6106. ; 101:33, s. 6484-
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Tidskriftsartikel (refereegranskat)abstract
- The reduction of NO with CO and H2 is shown to comprise two basic reactions: a surface oxygen abstraction by the reducing agent and a reoxidation of the surface by NO. The former reaction step has been demonstrated by transient CO2 formation during CO exposure of oxidized CaO surfaces, while the latter was demonstrated by N2 and/or N2O transient formation during NO exposure of a prereduced CaO surface. It was shown that at low temperatures (between room temperature and 500 °C) both N2 and N2O were formed, but at temperatures above 500 °C only N2 was observed. The activation energies of the respective steps have been determined using temperature-programmed reaction experiments. The activation energy of the surface oxygen abstraction was determined to be 25 kcal/mol and is similar to the apparent activation energy of the overall reaction. The activation energy of the NO bond breakage was determined to be maximum 10 kcal/mol as measured by N2O formation. The importance of an N2O2- or N2O22- intermediate in the formation of N2O will be discussed, and the importance of N2O decomposition in forming N2 at temperatures above 500 °C will be compared with a N surface diffusion mechanism.
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| 4. |
- Gårdfeldt, Katarina, 1959, et al.
(författare)
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A kinetic study on the Abiotic Methylation of Divalent Mercury in the Aqueous phase
- 2003
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Ingår i: Science of the Total Environment. - 0048-9697 .- 1879-1026. ; 304:1-3, s. 127-136
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Tidskriftsartikel (refereegranskat)abstract
- The mechanism and kinetics of the formation of methylmercury from an experimental solution containing divalent mercury and acetic acid has been investigated. The experiments were performed in a 2-dm3 Teflon reactor. The organic mercury was measured with time resolutions varying between minutes and hours, after derivatisation, gas chromatography separation and Cold vapour atomic fluorescence detection. (GC)-CVAFS. CVAFS technique was used for determination of inorganic mercury in the aqueous phase using an automated mercury analyser. The experiments were carried out in concentrations relevant for natural waters. Our result shows that the reaction proceeds via mercury acetate complexes. A first order reaction coefficient has been calculated at various pH values, and was found to be (9.0±0.9)×10−7 s−1 at pH 3.6–3.7. The rate was not found to be enhanced by UV-light when taking into account the photolytical degradation of methylmercury. The reaction rate at various pH values, the influences of some other relevant reaction parameters, and implications for atmospheric and terrestrial waters are discussed.
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| 8. |
- Gårdfeldt, Katarina, 1959, et al.
(författare)
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Evasion of Mercury from coastal and open waters of the Atlantic ocean and the Mediterranean sea
- 2003
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Ingår i: Atmospheric Environment. - 1352-2310 .- 1873-2844. ; 37:Suppl 1
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Tidskriftsartikel (refereegranskat)abstract
- Dissolved gaseous mercury (DGM) was measured in coastal Atlantic seawater and in the Mediterranean Sea. The Atlantic measurements were performed during September 1999 at the Mace Head Atmospheric Research Station, situated on the Irish west coast. The measurements in the Mediterranean Sea were made along a 6000 km cruise path from 14 July to 9 August 2000 in the framework of the Med-Oceanor project. Total gaseous mercury (TGM) concentrations in air were continuously measured with a 5 min time resolution using an automated mercury analyser (Tekran 2537A) during both expeditions. Paired TGM and DGM samples from all campaigns showed that the surface water was supersaturated with elemental mercury. The mercury evasion was estimated using a gas exchange model (J. Geophys. Res. 97 (1992) 7373), which uses salinity, wind speed and water temperature as independent parameters. The predicted average mercury evasion from the coastal Atlantic water was 2.7 ng m−2 h−1 implying that the concentration of TGM in the Atlantic air is enhanced by mercury evasion from the sea. Measurements in different regions of the Mediterranean Sea showed spatial variations in DGM concentrations. The highest DGM concentration (90 pg l−1) was observed at a location in the Strait of Sicily (37°16N 11°52E). The mercury evasion in the eastern sector of the Mediterranean Sea (area: 32–36°N, 17–28°E) was generally higher (7.9 ng m−2 h−1) than that observed in the Tyrrhenian Sea (4.2 ng m−2 h−1) or in the western sector (2.5 ng m−2 h−1) (areas: 38–42°N, 8–13°E and 38–41°N, 7–8°E, respectively). Estimations of mercury evasion were also made at Mediterranean coastal sites using a dynamic chamber technique. In addition, a newly developed method making continuous in situ DGM measurements possible was tested.
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| 9. |
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| 10. |
- Gårdfeldt, Katarina, 1959, et al.
(författare)
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Oxidation of atomic mercury by hydroxyl radicals and photoinduced decomposition of methylmercury species in the aqueous phase
- 2001
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Ingår i: Atmospheric Environment. - 1352-2310 .- 1873-2844. ; 35:17, s. 3039-3047
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Tidskriftsartikel (refereegranskat)abstract
- The rate constant for Hg0+.OH, kHg0+.OH=(2.4±0.3)×109 M−1 s−1, in the aqueous phase was determined using a relative rate technique with methyl mercury as reference compound. The .OH initiated mercury reaction proceeds via the molecular Hg(I) radical which is oxidised to Hg(II) by dissolved O2. The reaction can be of importance under certain atmospheric circumstances, such as when the aqueous phase capacity of forming OH radicals is significant and the gas phase concentration of ozone drops. The same end product, i.e. Hg(II) was observed from the photodegradation of methylmercury hydroxide. In this case, molecular Hg(I) radicals are again likely to be formed after photodegradation of the Hg–C bond with subsequent oxidation. A lifetime of 230 h of methylmercury at outdoor conditions was estimated due to this reaction. The action of .OH on methylmercury species also involves breaking of organometallic bonds and formation of Hg(II). Speciation of these reaction products from methylmercury is important for the estimation of biogeochemical cycling of mercury.
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