Quantitative Analytical Method for Single Rain Droplets via Crystal Formation in Photocrosslinking Polymer Gel.

Ion composition contained in individual rain droplets provides important information to investigate the chemistry in rain and clouds, but general rain sampling equipment temporally and spatially averages the information. Determination of the SO42- concentration in an individual rain droplet was achieved by precipitate production in synthesized acrylamide polymer gel. Concentration of the target ion was calculated from the droplet print diameter and precipitation area measured from digital microscope images. We investigated the effects of the interior electrolyte concentration in the polyacrylamide gel and UV irradiation time on the physical properties of the gel and precipitate formation. The precipitated components were identified by scanning electron microscopy with energy dispersive X-ray analysis. We also clarified the effects of coexisting ions on the reaction between the interior and exterior electrolytes. For actual rainwater, the SO42- concentration estimated by this method was in agreement with the results obtained by ion chromatography.

Preliminary study of quantitative analysis of ammonium ions in a raindrop following Liesegang ring formation.

NH(4)(+) concentration in an individual droplet was determined by forming a Liesegang ring on a gelatin film containing NaB(C(6)H(5))(4). The NH(4)(+) concentration (mol L(-1) abbreviated to M) was calculated from the NH(4)(+) amount (mol) ascertained in a droplet using pixel count measurements. The droplet volume (L) was calculated by measurement of the diameter of a droplet print on the gelatin film. For rainwater, the NH(4)(+) concentration estimated using this method corresponded with results obtained using ion chromatography.

Threshold for spontaneous oscillation in a three-phase liquid membrane system involving nonionic surfactant.

This study of self-oscillation was conducted using a new three-phase liquid membrane system of ethanol aqueous solution, benzyl alcohol solution with nonionic surfactant, and pure water. Relations of the initial ethanol concentration to the oscillation amplitude and frequency, and to the induction period before oscillations were investigated. The oscillation amplitude is independent of the initial ethanol concentration, but the frequency and the induction period are related to it. The oscillation frequency increased concomitantly with the increased ethanol initial concentration, but the induction period before the electrical oscillations decreased with increasing concentration. To estimate the influence of ethanol diffusion on the electrical oscillations, the ethanol concentration in each phase was measured using separate experiments after different durations of oscillation. The diffusion coefficient was calculated using Fick's second law. Results show successful estimation of the threshold for oscillations. The threshold is defined in terms of the ethanol concentration at the interface between the benzyl alcohol phase and the pure water phase.

Leaching of cell wall components caused by acid deposition on fir needles and trees.

Virgin fir forests have been declining since the 1960s at Mt. Oyama, which is located at the eastern edge of the Tanzawa Mountains and adjacent to the Kanto plain in Japan. An acid fog frequently occurs in the mountains. We collected throughfall and stemflow under fir trees and rainfall every week during January-December 2004 at Mt. Oyama to clarify the influence of acid fog on the decline of fir (Abies firma) needles. In relation to throughfall and stemflow, D-mannose, D-galactose, and D-glucose are the major neutral sugar components; only D-glucose is a major component of rainfall. The correlation coefficient between the total neutral sugars and uronic acid (as D-galacturonic acid), which is a key component of the cross-linking between pectic polysaccharides, was high except for rainfall. The leached amount of calcium ion, neutral sugars, uronic acid, and boron is related to the nitrate ion concentration in throughfall. Results of a laboratory exposure experiment using artificial fog water simulating the average composition of fog water observed at Mt. Oyama (simulated acid fog: SAF) on the fir seedling needles also shows a large leaching of these components from the cell walls of fir needles. The leaching amount increased concomitantly with decreasing pH of the SAF solution. We also observed that a dimeric rhamnogalacturonan II-borate complex (dRG-II-B) that exists in the cell wall as pectic polysaccharide was converted to monomeric RG-II (mRG-II) by the leaching of calcium ion and boron. Results not only of field observations but also those of laboratory experiments indicate a large effect of acid depositions on fir needles.

Growth and physiological responses of beech seedlings to long-term exposure of acid fog.

Seven-year-old beech seedlings (Fagus crenata) were exposed to simulated acid fog (SAF) at pH 3 or pH 5 (as control) prepared by adding a 2:1:1 mixture (molar ratio) of nitric acid, ammonium sulfate, and sodium chloride to ultrapure water from September 2004 to July 2006 in a mobile fog chamber. In comparison to control seedlings, seedlings from the pH 3 treatment displayed inferior plant height, stem diameter, number of leaves, and dry matter production, but greater leaf area. Furthermore, exposure to SAF induced early falling of leaves with a nearly two-times-greater normalized leaf number index than control. The starch levels in the stems of seedlings of the pH 3 treatment were much lower than those of control at the harvest. The acid fog-induced reduction of the starch accumulation is considered to occur mainly because of fewer leaves during the growth phase. Results of laboratory experiments demonstrate that the amount of base cations leached from the beech leaves increased with decreasing pH of SAF; the leaching amount of calcium ion from the beech was high relative to that of conifers such as fir and cedar. These results imply that chronic acid fog exposure suppresses growth and physiological activity of beech seedlings.

Application of liesegang ring formation on a gelatin film to the determination of sulfate concentration in individual rain droplets.

The determination of SO(4)(2-) concentration in individual rain droplets can be achieved using a gelatin film containing 5 mM barium chloride and 5 mM barium nitrate. SO(4)(2-) in droplets reacts with barium chloride in the film to form the characteristic Liesegang rings. The areal ratio of the ring to the droplet print (ARRD) on the film is a good indicator for determining the SO(4)(2-) concentrations in an individual droplet. Interference by NO(3)(-) in determining SO(4)(2-) concentration can be avoided by adding barium nitrate to the gelatin. Measurements of SO(4)(2-) in rainwater samples by this method agreed well with those from ion chromatography. The individual analysis of rain droplets by this method indicated that the concentrations of SO(4)(2-) were largely different with a 5-order magnitude, even among individual rain droplets collected simultaneously, and were higher in smaller rain droplets.

Severe leaching of calcium ions from fir needles caused by acid fog.

We have measured the components of the throughfall under fir trees (Abies firma) in the field around Mt. Oyama, where the forest appears to be declining, for the period 1994-1998. Exposure experiments of a simulated acid fog to fir twigs were performed under field conditions. There was a similarity between the acid response in the field and that in the laboratory. In both studies, the severe leaching of calcium ions from the needle surface was caused by exposure to acid fog. We also applied acid fog to fir seedlings over 1 year and observed a decrease in the growth of the seedlings due to this application in the dormant season. These results suggest that the severe leaching of calcium ions due to acid fog may cause the deficiency of calcium and be responsible for the decline of the fir trees.

High frequency and large deposition of acid fog on high elevation forest.

We have collected and analyzed fogwater on the mountainside of Mt. Oyama (1252 m) in the Tanzawa Mountains of Japan and observed the fog event frequency from the base of the mountain with a video camera. The fog event frequency increased with elevation and was observed to be present 46% of the year at the summit. The water deposition via throughfall increased with elevation because of the increase in fogwater interception and was about twice that via rain at the summit, where the air pollutant deposition via throughfall was several times that via rainwater. The dry deposition and the deposition via fogwater were dominant factors in the total ion deposition at high elevation sites. In a fog event, nitric acid, the major acid component on the mountain, is formed during the transport of the air mass from the base of the mountain along the mountainside, where gases including nitric acid deposit and are scavenged by fogwater. Therefore, high acidity caused by nitric acid and relatively low ion strength are observed in the fogwater at high elevation sites.