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Annual Report 2003    
  Research Overview and Topics in 2002
   Chemical Analysis Research Center   
       

The Chemical Analysis Research Center consists of 2 laboratories. The mission of the Environmental Chemicals Analysis Laboratory is the development of rapid and highly precise methods for the analysis of dioxins, pesticides, and endocrine disrupters such as nonylphenols and heavy metals, and for elucidation of the behavior and pathways of chemicals in the agricultural environment. We have developed methods for the simultaneous determination of 15 sulfonylurea herbicides and the rapid screening of metalloproteins (Topic 1). We are also studying enzyme-linked immunosorbent assay of nonylphenols.

The Radioisotope Analysis Laboratory has been measuring the radioactivity of artificial and natural radioisotopes such as 137Cs and 90Sr in wheat, rice, and soil since 1957. The other research objective of this laboratory is the development of a rapid and highly accurate method for the analysis of agro-environment elements by using radiation, and elucidation of the dynamics of radionuclides and relation nuclide (Topics 2 and 3).

Dr. Eun Heesoo, a researcher at the Environmental Chemicals Analysis Laboratory, was awarded a "Gratitude Plate" by Chung Moo-Nam, administrator of the Rural Development Administration of the Korean Government, for his outstanding contributions to the advancement of agricultural research and development.

Topic 1: Rapid screening of metalloproteins by LA-ICP-MS combined with Native-PAGE

About one-third of all proteins contain metal ions such as calcium, iron, zinc, and copper and are therefore called metalloproteins. Most metalloproteins play important roles in biological activities as enzymes, and some of them facilitate the detoxification of toxic metal ions such as cadmium and mercury. To understand the structure and function of metalloproteins, we need to develop analytical methods that have high resolution for proteins and high sensitivity for metal ions. For this purpose we trialed a combination of native polyacrylamide gel electrophoresis (Native-PAGE) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Standard metal-containing proteins - horse ferritin, bovine catalase, bovine albumin, egg albumin, cytochrome C, rabbit metallothionein, and keyhole limpet hemocyanin - were separated by using Native-PAGE. After staining with Coomassie blue, the gel was dehydrated by soaking in ethanol-water solution. The volume percentage of ethanol was raised stepwise from 50% to 100%. The shrunken gel was air-dried and the metal ions were analyzed by LA-ICP-MS. Metal ions were detected accurately in all the standard proteins (Fig. 1). Furthermore, unexpected metal ions such as cadmium in ferritin were detected. This method could be useful for rapid screening of various metal-containing proteins and their mixtures. (K. Baba)

Topic 2: Assessment of desertification from soil concentrations of radioactive nuclides

In recent years, overgrazing and excessive cultivation have been causing desertification in the grasslands of China's Inner Mongolia Autonomous Region, and this has become a grave problem. The purpose of this research is to develop techniques to assess surface erosion from the concentrations of radioactive nuclide fallout in soil. We studied a new technique that uses the naturally occurring radioactive nuclide 210Pb. This nuclide belongs to the uranium series and is produced by the disintegration of 238U in rocks and soil, through the intermediate forms 226Ra and 222Rn:

  238U ----> 226Ra ----> 222Rn ----> 210Pb ----> 206Pb
Half-life:   4.5 billion years   1600 years   3.8 days   22.3 years  

These nuclides are in radioactive equilibrium, so the ratios of their remaining amounts are constant. However, the rare gas 222Rn comes between 226Ra and 210Pb, and this nuclide disperses from the soil into the atmosphere, although in small ratios. This dispersed 222Rn disintegrates into 210Pb, which then falls to earth, where it accumulates when fine soil particles adsorb it. We marked off areas of grassland as test areas in which we controlled grazing and investigated the relationship between the concentration of fallout 210Pb radioactivity in the soil, the topographical conditions, and the grazing pressure.

Figure 2 shows the shapes of the test zones and their elevation distributions from the survey results. Although the topography was more or less flat, the southern parts were a little higher, and we found a maximum elevation difference of about 3 m within the entire test area. Different grazing densities were set for each zone, and sheep were continually pastured there from 1992 to 1996. In 1998 we took samples of the soil down to a depth of 5 cm at several locations in each of the test zones. After drying the samples, we measured their gamma radiation with a germanium semiconductor detector to find their radioactivity concentrations.

Figure 3 shows the distribution of fallout of 210Pb radioactivity in the soil of the test grazing zones. We compared the grazing zones and discovered that the higher the grazing density and the greater the degradation of vegetation by grazing, the more locations we found with low 210Pb radioactivity concentrations. Bare land appeared on the hillocks, where the elevation was higher, and locations with low 210Pb concentrations were also distributed mainly among the hillocks. Therefore, this method of estimating the extent of erosion by using fallout of 210Pb in the soil as an indicator is useful for assessing desertification, and is promising for applications such as judging the risk of desertification and confirming the effectiveness of afforestation and other remedial measures. (H. Fujiwara)

 
 

Topic 3: Comparison of vertical distributions of iodine in soils of a paddy field, an upland field, and a forest plot

Iodine is an essential component of thyroid hormones, and about 200 million people worldwide suffer goiter because of a deficiency of this element. Iodine, however, is highly toxic to higher plants. The Chernobyl disaster of 1986 sent large quantities of 131I (half-life 8 days) streaming into the environment. Further, 129I (half-life 15.7 million years) can be released from nuclear fuel reprocessing facilities, so it is important that a 129I monitoring system be installed in the facility under construction at the village of Rokkasho, Japan.

To study the fate of iodine in the environment, we considered the vertical distribution of iodine in the soil to a depth of 50 m in a paddy field, an upland field, and a forest plot situated in a diluvial upland at NIAES.

The soil iodine concentrations to 2 m ranged from forest plot > upland field >> paddy field. In the upland field, the iodine concentrations (in mg kg-1 dry weight) of the surface layers and the next layer (the Ap1, Ap2, and 1A1 horizons, 0-30 cm) were the highest (42-44), and in the forest plot the iodine concentrations of the surface layers and the next layer (Ap, A, and AB horizons, 0-29 cm) were the highest (65-71). In the paddy field, the surface layer (Apg horizon, 0-18 cm) (the most reducing horizon), was eluvial with regard to iodine and featured a low content of 2.8; the iodine concentration (5.3) of the slightly oxidizing Bg1 horizon (18-36 cm) was higher than that of the surface layer, and the iodine concentration (12) of the 2Bw horizon (60-89 cm), which lacked gleyzation, was highest. From the depth at which the first aquiclude (composed of heavy clay) appeared, to the depth at which the second aquifer (composed primarily of sand and fine sand) appeared, the iodine concentration rapidly decreased to very low level of around 0.1 on 3 sampling locations. There was little difference between the 3 sampling locations in terms of the zones at, and beneath, the reductive second permeable layer, situated below the water table (Fig. 4). In the second aquiclude, which contained mostly clay and silt, the iodine concentration increased with depth and reached 5 mg kg-1 on 3 sampling locations. The layers from the third permeable layer to the third aquiclude were more reducing and had a higher pH, which promoted the elution of iodine at levels ranging from 0.02 to 1.0. There, the iodine level on 3 sampling locations was low, and there was little difference between the levels in the permeable portions and those in the third aquiclude. These results are useful for forecasting the behavior of radioactive iodine in the environment. (N. Kihou)


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