Dimethylsulfide （DMS） is generally thought to be lost from the surface oceans by evasion into the atmosphere as well as consumption by microbe. However, photochemical process might be important in the removal of DMS...Dimethylsulfide （DMS） is generally thought to be lost from the surface oceans by evasion into the atmosphere as well as consumption by microbe. However, photochemical process might be important in the removal of DMS in the oceanic photic zone. A kinetic investigation into the photochemical oxidation of DMS in seawater was performed. The photo-oxidation rates of DMS were influenced by various factors including the medium, dissolved oxygen, photosensitizers, and heavy metal ions. The photo-oxidation rates of DMS were higher in seawater than in distilled water, presumably due to the effect of salinity existing in seawater. Three usual photosensitizers （humic acid, fulvic acid and anthroquinone）, especially in the presence of oxygen, were able to enhance the photo-oxidation rate of DMS, with the fastest rate observed with anthroquinone. Photo-oxidation of DMS followed first order reaction kinetics with the rate constant ranging from 2.5 × 10^-5 to 34.3 × 10^-5. Quantitative analysis showed that approximately 32% of the photochemically removed DMS was converted to dimethylsulfoxide. One of the important findings was that the presence of Hg^2 ＋ could markedly accelerate the photo-oxidation rate of DMS in seawater. The mechanism of mercuric catalysis for DMS photolysis was suggested according to the way of CTTM （ charge transfer to metal） of DMS - Hg^2＋ complex.展开更多
Kinetic investigation into the phogochemical oxidation of benzothiophene in seawater showed that photo-oxidation rates of benzothiophene were influenced by the medium,pH,heary metal ion,dissolved oxygen,and light inte...Kinetic investigation into the phogochemical oxidation of benzothiophene in seawater showed that photo-oxidation rates of benzothiophene were influenced by the medium,pH,heary metal ion,dissolved oxygen,and light intensity.The photo-oxidation of benzothiophene followed the first order reaction law, with the rate constants ranging from 1.21×10 -5 /s to 5.38×10 -5 /s.An interesting observation was that the presence of Hg 2+ could markedly enhance the photo-oxidation rate of benzothiophene in seawater;and that the photo-oxidation rate of benzothiophene increased with light intensity.The effect of oxygen on the rate constant for benzothiophene photolysis was also observed.Compared with purging with nitrogen,purging seawater with oxygen evidently increased the photolysis rate of benzothiophene. Based on this observation,a benzothiophene photo-oxidation mechanism including singlet oxygen (O 2 1 Δ g) was suggested.Two photolysis products of benzothiophene were identified.The photolysis of benzothiophene is considered to be important in the removal of this compound in seawater.展开更多
基金We greatly acknowledge the support provided for this research by the National Natural Science Foundation of China under contract Nos 40476034,40525017 and 40490265We are also grateful for the support of Key Project of Ministry of Education,China under contract No.105105+1 种基金the Program for New Century Excellent Talents in University,Ministry of Education under contract No.NCET-04-0643Taishan Mountain Scholar Construction Engineering Special Fund of Shandong Province,China.
文摘Dimethylsulfide （DMS） is generally thought to be lost from the surface oceans by evasion into the atmosphere as well as consumption by microbe. However, photochemical process might be important in the removal of DMS in the oceanic photic zone. A kinetic investigation into the photochemical oxidation of DMS in seawater was performed. The photo-oxidation rates of DMS were influenced by various factors including the medium, dissolved oxygen, photosensitizers, and heavy metal ions. The photo-oxidation rates of DMS were higher in seawater than in distilled water, presumably due to the effect of salinity existing in seawater. Three usual photosensitizers （humic acid, fulvic acid and anthroquinone）, especially in the presence of oxygen, were able to enhance the photo-oxidation rate of DMS, with the fastest rate observed with anthroquinone. Photo-oxidation of DMS followed first order reaction kinetics with the rate constant ranging from 2.5 × 10^-5 to 34.3 × 10^-5. Quantitative analysis showed that approximately 32% of the photochemically removed DMS was converted to dimethylsulfoxide. One of the important findings was that the presence of Hg^2 ＋ could markedly accelerate the photo-oxidation rate of DMS in seawater. The mechanism of mercuric catalysis for DMS photolysis was suggested according to the way of CTTM （ charge transfer to metal） of DMS - Hg^2＋ complex.
文摘Kinetic investigation into the phogochemical oxidation of benzothiophene in seawater showed that photo-oxidation rates of benzothiophene were influenced by the medium,pH,heary metal ion,dissolved oxygen,and light intensity.The photo-oxidation of benzothiophene followed the first order reaction law, with the rate constants ranging from 1.21×10 -5 /s to 5.38×10 -5 /s.An interesting observation was that the presence of Hg 2+ could markedly enhance the photo-oxidation rate of benzothiophene in seawater;and that the photo-oxidation rate of benzothiophene increased with light intensity.The effect of oxygen on the rate constant for benzothiophene photolysis was also observed.Compared with purging with nitrogen,purging seawater with oxygen evidently increased the photolysis rate of benzothiophene. Based on this observation,a benzothiophene photo-oxidation mechanism including singlet oxygen (O 2 1 Δ g) was suggested.Two photolysis products of benzothiophene were identified.The photolysis of benzothiophene is considered to be important in the removal of this compound in seawater.
