Adsorption of 1-decyl-3-methylimidazolium bromide and solvation structure of bromide at the air/water interface.

The adsorbed film of 1-decyl-3-methylimidazolium bromide (DeMIMB) at the air/water interface was investigated employing the surface tension measurement and the x-ray absorption fine structure method under the total reflection condition (TRXAFS). From the surface tension measurement, the surface excess concentrations of ions were determined. From the XAFS measurement, two solvation states of bromide ion were found in the adsorbed film, which were assigned to be "free-Br" and "bound-Br". The hydration number of the former was estimated to be 6 while that of the latter was estimated to be 4. The results based on the XAFS analysis provided significant information on the formation of domains in the adsorbed film; the most conceivable situation is that the adsorbed molecules are definitely not homogeneously dispersed, but domains (islands or clusters) are dispersed in the adsorbed film. A regular and rather tight stacking of immidazolium rings may be formed in the domains.

Discrimination of ionic pollutants except condensation nuclei of acid fog using an ultrasonic humidifier.

Fog droplets in the atmosphere are first produced by the activation of cloud condensation nuclei (CCN), which are originally some ionic compound. Subsequently, the nuclei grow by vapor diffusion. Fog droplets are polluted through the activation process and successive diffusion growth and residence (post activation). We cannot distinguish the effects of the two pollution processes of natural fog water samples. We found that fog droplets can be produced artificially without CCN using an ultrasonic humidifier. Because the artificial fog droplets are not polluted by CCN, the movement of the fog droplets in natural air will take up some pollutants in the air. Consequently, the two pollution processes of fog (the activation of CCN and the post activation process) can be discriminated using data from field experiments. This sampling analytical method is extremely important for further research regarding fog, clouds and environmental chemistry.

Zinc(II) porphyrins at the air-water interface as studied by polarized total-reflection X-ray absorption fine structure.

The polarized total-reflection X-ray absorption fine structure method was applied to characterize zinc porphyrins at the air-water interface. The X-ray absorption near edge structure exhibited a significant difference depending on the polarization of the X-ray. A shoulder peak of the Zn K-edge corresponding to the 1s-4p(z) transition for a square planar metal complex without axial coordination(s) was observed at 9662 eV, which indicates that the axial coordination sites of zinc porphyrin molecules examined are not fully hydrated at the air-water interface. The molecular orientation of zinc porphyrins was determined by analyzing the polarization dependence of the transition peak intensity. The meso-substituted porphyrin derivative 5,10,15,20-tetraphenylporphyrinatozinc(II) (ZnTPP) orients rather parallel to the solution surface. In contrast to ZnTPP, the zinc(II) protoporphyrin IX (ZnPP) with hydrophilic carboxyl groups at one side of the molecule stands up with respect to the solution surface, and the average tilting angle of the porphyrin plane to the surface was evaluated to be between 57 degrees and 43 degrees. In addition, the axial coordination of ZnPP is modified depending on the surface concentration, in which the axial hydration to the zinc center is effectively inhibited in the compressed surface layer.

Photoinduced electron transfer of 5,10,15,20-tetraphenylporphyrinato zinc(II) at the polarized water/1,2-dichloroethane interface.

The photocurrent at the polarized water/1,2-dichloroethane (DCE) interface was successfully observed in the presence of a lipophilic sensitizer, 5,10,15,20-tetraphenylporphyrinato zinc (ZnTPP), in the organic phase. The photocurrent transient responses were apparently affected by the employed organic supporting electrolyte: tetrapenthylammonium tetraphenylborate (TPnATPB) or tris(tetraoctylammonium)tungstophosphate ((TOcA)3PW12O40). The photocurrent measured in the TPnATPB system exhibited rather slow responses associated with the ion transfer of photoproducts. On the other hand, the photoinduced heterogeneous electron transfer could be observed in the use of (TOcA)3PW12O40. The photocurrent intensity in the (TOcA)3PW12O40 system exhibited an apparent pH dependence and the photoreduction of hydrogen ions probably took place at the water/DCE interface. By analyzing the real and imaginary components of the photocurrent depending on the photoexcitation frequency, we roughly estimated the phenomenological rate constants of the product separation (k(ps)) and recombination (k(rec)) processes as log(k(ps)/s(-1)) = 1.5 +/- 0.2 and log(k(rec)/s(-1)) = 1.8 +/- 0.1, respectively.

Effect of long-range transport of air mass on the ionic components in radiation fog in northern Japan.

Water samples from radiation and upslope types of fog were collected at Takanosu Basin and Hachimantai mountain range of Akita Prefecture in northern Japan, respectively. The effect of the long-range transport of pollutants from the Asian Continent to the basin and the mountain range on the chemical characteristics of two types of fog was studied using chemical analysis data for the water samples as well as the back-trajectories of the air mass. In particular, non-sea-salt (nss)-SO4(2-) of radiation fog provided a much higher concentration than that of upslope fog, which suggests that nss-SO4(2-) might be transported mainly from the Asian Continent. The transport and uptake mechanism of pollutants in the radiation fog water were explained based on their accumulation in the basin due to anticyclonic subsidence and by the long-lasting fog behavior.