Characteristics of Nitrogenous Air Pollutants at Urban and Suburban Forested Sites, Western Japan

Nitrogenous air pollutants including nitrogen dioxide (NO₂), nitric acid (HNO₃), nitrate (NO ₃ ^? ), ammonia (NH₃), ammonium (NH ₄ ⁺ ), and nitrous acid (HONO) were characterized at an urban forested (UF) site in Hiroshima and at a suburban forested (SF) site in Fukuoka, western Japan, using an annular denuder system for 1?year from May 2006 to May 2007 to compare the concentrations and chemical species of atmospheric nitrogenous pollutants between UF and SF sites. The proximity of the urban area was reflected in higher NO₂ concentrations at the UF site than at the SF site. NO₂ was more oxidized at the SF site because it is farther from an urban area than the UF site, which was reflected in higher concentrations of HNO₃ at the SF site than the UF site. HNO₃ and acidic sulfate is neutralized by NH₃, existing as ammonium nitrate (NH₄NO₃) and ammonium sulfate [(NH₄)₂SO₄] at the UF site. At the SF site, acidic sulfate is neutralized by NH₃, existing as (NH₄)₂SO₄, but NH₄NO₃, had scarcely formed at the SF site. A much higher HONO concentration was observed at the UF site than at the SF site, especially in winter and spring at night, which could be explained by higher NO₂ concentrations at the UF site because of its proximity to an urban area and stagnant meteorological conditions. Atmospheric HONO determination was critical in evaluating the possibility of damage to trees in UF areas.     

Expression of canine Kdap in normal, hyperplastic and neoplastic epidermis

Keratinocyte differentiation-associated protein, Kdap, is a recently identified small secretory protein that may act as a soluble regulator for the cornification and/or desquamation of keratinocytes. To clarify the role of Kdap in the terminal differentiation of keratinocytes, detailed in situ localisation of Kdap was studied using canine skin with normal, hyperplastic and neoplastic epidermis. In normal canine trunk skin, Kdap was expressed by granular keratinocytes, with polarity to the apical side of the cells, suggesting that canine Kdap is present in lamellar granules, as in humans. Expression of Kdap was widespread in the spinous layers in hyperplastic epidermis, but was undetectable in squamous cell carcinomas. These findings suggest that Kdap is closely related to the delay of terminal differentiation and/or release of cells in hyperplastic epidermis.     

The determination of 1,2-dicarboxylate structures in humic acid by fluorescein formation

To detect and quantify 1,2-dicarboxylate structures in humic acid, a chemical reaction forming fluoresceins from 1,2-dicarboxylates and resorcinol was tested. Resorcinol reacted with humic acid to form products having absorption maxima at about 490 nm. A procedure was then developed for quantitative analysis of the radicals. Eight humic acid samples tested contained 0.4–1.0 mmol/g of 1,2-dicarboxylate structures. The 1,2-Dicarboxylates detected in humic acid were considered as ophthalate homologs.     

Conversion of dextran to cycloisomaltooligosaccharides using an enzyme-immobilized porous hollow-fiber membrane

This paper describes a cycloisomaltooligosaccharide glucanotransferase (CITase)-multilayer-immobilized porous hollow-fiber membrane used as an enzyme bioreactor. Dextran, a substrate with an average molecular mass of 43000, is converted into seven- to nine-glucose-membered cycloisomaltooligosaccharides, effective as a preventive for dental caries, aided by convective transport of the substrate to the vicinity of the enzyme through the pores. Epoxy-group-containing graft chains were uniformly appended onto the surface of pores throughout a porous hollow-fiber membrane by radiation-induced graft polymerization. Subsequently, a diethylamino group was introduced, as an anion-exchange moiety, to the graft chains, which caused the chains to expand toward the interior of the pores due to mutual electrostatic repulsion. The expanding graft chain provided multilayer binding sites for CITase. Fifty-five milligrams of adsorbed CITase per gram of membrane is equivalent to the degree of multilayer binding of 5. Finally, 80% of the multilayer-adsorbed CITase was immobilized via enzymatic cross-linking with transglutaminase to prevent the leakage of enzymes. CITase, with a degree of multilayer immobilization of 4, produced the target cycloisomaltooligosaccharides at a conversion yield of 55% in weight at 310 K during permeation by the dextran solution at a space velocity defined as the permeation rate divided by membrane volume of 6 per hour.     

Sapflow characteristics and climatic responses in three forest species in the semiarid Loess Plateau region of China

In the semiarid Loess Plateau region of China, ecosystems are frequently affected by water shortages. Late spring and early summer are periods when forest communities tend to suffer from soil drought. To clarify the water-use strategies of the main species in this area, the xylem sap flow of trees from three species in the field was monitored for three successive periods in summer using Granier-type thermal dissipation probes. Vapor pressure deficit (VPD), solar radiation (R_s) and soil moisture had varying influences on sap flux density (F_d) in the species. Normalized F_d values could be fitted to VPD using an exponential saturation function, but the fit was better with a derived variable of transpiration (VT), an integrated index calculated from VPD and R_s. From differences in model coefficients, the species were roughly divided into two types with contrasting drought sensitivity. The exotic Robinia pseudoacacia was defined as drought-sensitive type. It showed higher sapflow increases in response to rainfall, suggesting a high water demand and high influence of soil water conditions on transpiration. This species showed relatively late stomatal response to increasing VPD. The wide-peak pattern of diurnal sapflow course also suggests relatively low stomatal regulation in this species. The drought-insensitive type consisted of the naturally dominant Quercus liaotungensis and an indigenous concomitant species, Armeniaca sibirica, in the forest. The sap flow of these species was not very sensitive to changes in soil water conditions. The results suggest that typical indigenous species can manage the water consumption conservatively under both drought and wet conditions. Variations in water use strategies within indigenous species are also detected.     

Chromatographic Separation of Green Humic Acid from Podzol Humus

One of the authors, Kumada ¹⁾ has found that absorption spectra of podzol humic acids, remarkably different from the other soil humic acids, have fairly distinct absorption bands near 620, 570 and 450 mµ, and he tentatively named them. P type humic acid. P type humic acid seems specific not only in its visible absorption spectra, but also in infra. red absorption spectra, in susceptible to electrolytes, etc. The authors are now engaged in the study of the nature and properties of P type humic acid, and recently they have found that it is composed of at least two main fractions, the one is reddish brown, and the other green, in alkaline solution. The experimental results are briefly presented.     

Elementary composition of humic acids

The author made a study of the elementary composition of various humic acids; L and SrL humic acids used in the previous report¹⁾, and two lowmoor humic acids.     

The infra-red spectra of humic acids

It is well krown that many investigations have been presented on the visible and ultraviolet absorption spectra of soil humic acids, and they contributed greatly to our knowledge on the nature of humus. On the other hand, there have been very few works on the infared spectra of humic acids, though it is expected that they would give us useful information on their nature, especially furctional groups.     

Susceptibility of humic acid towards sodium amalgam

Three humic acids (HA-I) of different degrees of humification were treated with HCl (1:1). The hydrolyzed humic acids (HA-II) were subsequently degraded with Na-amalgam. The reduction products were divided into the following fractions: humic acid residues (HA-III), fulvic acid (FA), and ether-extractable lubstances (Et),

The humic acids used in this study were extracted from the following three soils; Inogashira (Volcanic ash soil), Kuragari (Drown forest soil, B_D type), and Higashiyama (Brown forest soil, rB_B type).

The experimental results are summarized as follows:

1. The RF values of HA-II, in the case of Inogashira and Kuragari, were higher, and the △log K values were lower than those of HA-I. The carbon and oxygen contents of HA-II were higher while the hydrogen, and nitrogen contents were lower than those of HA-I.

2. The total amount of carbon in HA-III. FA and Et added up to about 90% of the carbon present in HA-II. The carbon of HA-III found in HA-III after reduction tended to increase in the order: Inogashira>Kuragari>Higashiyama. In FA and Et, the opposite trend was followed.

In the case of Inogashira about 60% of the carbon of HA-II was found in HA-III.

3. The dark coloration of humic acid largely disappeared during the reductive treatment. As for the amorphous carbon-like structure detected in Inogashira, it was not found in the HA-III after reduction.

Therefore, it was presumed that the structures destroyed or saturated during the reductive treatment were the ones responsible for the essential properties of humic acid.     

Aromatic constituents of humic acids released by na-amalgam reductive cleavage,koh fusion and zinc dust fusion

Eight humic acids showing different degree of humification were treated with HCI (1:1). The hydrolyzed humic acids were subjected to reductive cleavage with Na-amalgam, KOH fusion and zinc dust fusion. The yields of degradation products were determined by colorimetry gas chromatography.

The perimental results Were summarized as follows:

l. The amounts of ether-soluble substances obtained by reductive cleavage with Naamlagan ranged from 21.6% for Kuragari (A type) to 7.8% for Kisokoma B₂ (Rp type). The yields of phenolic substances expressed in terms of vanillic acid content ranged from 3.0% for Kuragari (A type) to 1.8% for Kisokoma B₂ (Rp type). Resorcinol. p.hydroxybenzoic acid, vanillic acid, protocatechuic acid and syringic acid were detected in the gas chromatograms of the ethe-soluble substances and their total yield comprised less than 0.6% of the Kisokoma F (Rp type).

2. The KOH fusion of humic acid yielded a larger amount of degradation products as compared to reductive cleavage. The amount of ether-soluble substances ranged from 42.7% for Kisokoma F (Rp type) to 12.6% for Sochiken 1 (A type). The yields of phenolic substances, expressed in terms of amount of protocatechuic acid, ranged from 10.6% for Kisokoma F (Rp type) to 4.6% for Inogashira (A type). Exept for syringic acid, the same compounds released after ramged from 2.1% for Sochiken 2 (B type) to 0.4% for Sochiken 1 (A type).

3. The amounts of benzene-soluble substances and hydrocarbons obtained from Goshikigahara (P type) by zinc dust fusion were 20.9% and 5.2%, respectively. The yields of the hydrocarbons tended to increase in the order; P type > Rp type ≥ B type. Perylene and 2-methylanthracene were detected in the gas chromatograms of the hydrocarbons fractions and, in the case of Goshikigahara (P type), their yields were 0.031% and 0.010%, respectively.