A model for a type humic acid

In the preceding papers (1,2,3,4), the author studied some chemical properties of soil humic acids, and compared various so-called artificial humic acids with soil humic acids in respect to their absorption spectra and stabilities. According to these experimental results, it is Presumed that soil humic acids, especially A type, must contain not only benzene ring, but also condensed aromatic rings as their structural units.     

The infrared absorption spectra of soil components

In the preceding paper (1), the authors had determined the infrared absorption spectra of humic acids obtained from various soils of different origin, and concluded that they were, according to their infrared characteristics, classified into four groupes, i.e., A,B,Rp, and P types. After that, the authors conducted some experiments of the infrared spectra of soil components in order to get some information on the nature of so-called humin, and forms of soil clay and clay humus complex. The infrared spectra of silica, sesquioxides, clay minerals and humates of aluminium, iron and calcium were also determined for comparison. These experimental results will be given in this paper.     

Sephadex gel fractionation of humic acids

Using Sephadex G 50 gel filtration, three soil humic acids were separated into two to four fractions, which differed more or less in their spectrophotometric properties. The distribution of a humic acid fraction on an RF-Δlog K diagram was classified into two cases; in the first case, the RF increased and Δlog K decreased with the elution order, and in the second case, humic acid fractions distributed clockwise around the original humic acid.

A small amount of B type humic acid was separated by gel filtration from newly formed Rp type humic acid obtained from the mixtures of grass and soil materials incubated for four months under alternate field and air-dry conditions.     

Hydroxyanthraquinones in soil

(1) Seven hydroxyanthraquinone pigments were separated from Sochiken soil 1 (Kuroboku soil). Chrysotalunin, chrysophanoi, chrysazin, and skyrln were identified by spectroscopy and co-chromatography with authentic compounds. The presence of oxyskyrin was presumed by spectroscopy and color reactions.

(2) A homologue of 4,9-dihydroxyperylene-3, 10-quinone was also detected.

(3) The amounts of hydroxyanthraqulnones in eight soils of different types were determined by colorimetry using chrysotalunin as a standard pigment. Their amounts varied from 3 to 11 ppm.

(4) The main pigment extracted from most soils was chrysotalunin, though it was not detected in Miyahara, Higashiyama, and Kisokoma soils.     

Browning of pyrogallol as affected by clay minerals

One of the authors, Kumada(1), has presented the idea that humification must be regarded as browning phenomena of organic matter in soils. The browning reaction can be accelerated non-enzymatically as well as enzymatically, and it is considered that humification would be conducted under the influence of some catalytic actions of clay fraction, composed of various kinds of clay minerals, free oxides and electrolytes, as well as soil enzymes, under the prevailing hydrothermal conditions. This was well illustrated by Kyuma and Kawaguchi(2), who definitely demonstrated the catalytic effect of allophane on the oxidative polymerization of polyphenols.     

On the fractionation of humic acids by a fractional precipitation technique

When humic acid is investigated from the standpoint of high polymer chemistry, its fractionation is one of the most important and interesting problems. In this paper, some experimental results will be reported on the fractionation of humic acid by the fractional precipitation technique proposed by SCHULZ (I), which had been successfully applied on a soil humic acid by KYUMA (2).     

Humus composition of mountain soils in Central Japan with special reference to the distribution of P type humic acid

The central districts of Japan are mountainous areas rising to 3,000 metres which are predominantly covered with forest vegetation. A comprehensive and systematic classification of the soils in this region has not yet been made, but the following soil types have been reported to occur: - 1. 1. Brown forest soils, podzolic soils, black soils and red soils. [Described by OHMASA (14)]

2. 2. Alpine grassland soils and alpine meadow soils. [Described by KUMADA et al. (9)]

3. 3. A series of randzina-like soils with a very restricted distribution. These are derived mainly from limestone and show various degrees of maturity. [Described by KUMADA et al. (8)]

4. 4. Red-yellow soils. These sometimes show a close resemblance to OHMASA's red soils and are found on diluvial plateaux and hills. [Described by KANNO (1)]

5. 5. Paddy soils.

     

Studies on the properties of organic matter in buried humic horizon derived from volcanic ash

Abstract

Humic acids were extracted from the surface horizon Yu 1 and buried humic horizons (Yu 2, 800-864 AD; Yu 4, ca. 4,000 years B.P.; Yu 6, 7,000 years B.P.; Yu 7, ca. 10,000 years B.P.). The humic acids were filtered with ultramembranes with 20, 10, 5, 1 or 0.1 × 10' M.W. in this order and separated into five fractions; (>20), (20-10), (10-5), (5-1) and (1-0.1) × 10⁴ M.W. fractions. The elementary composition, functional groups, optical properties, and hydrolyzable total- and sugar-carbon contents of each humic acid fraction were determined, and the changes in properties of the humic acid with age after burial were discussed.

In horizons Yu 1 to Yu 6, the patterns of M.W. distribution of the >20 × 10⁴ to (1- 0.1) × 10⁴ fractions were rather similar. In contrast, Yu 7 was characterized by the predominance of (1-0.1) x 10' M.W. fraction and the presence of a small amount of <0.1 × 10⁴ M.W. fraction.

The chemical properties of humic acid (HA) fractions of each humic horizon and their changes with age after burial were as folIows:

1) Elementary composition of HA fractions of each humic horizon was rather similar to each other. The C% and C/N ratio increased, and the H%, N% and H/C ratio decreased in all HA fractions with age.

2) Total acidity and carboxyl contents of HA fractions of Yu 1 were higher in the lower M.W. fractions. These values increased with age up to Yu 4 or Yu 6 horizons, then decreased in the Yu 6 or Yu 7 horizon. The contents of carbonyl groups in all the HA fractions which were very low in Yu 1, showed a wide range of variations in Yu 2, intermediate values from Yu 4 to Yu 6 horizons then decreased in the HA fractions of Yu 7, except for the (>20) fraction.

3) The degree of humification of the HA fractions of Yu 1 judging from the RF and \sDlogK values, tended to be higher in higher M.W. fractions, and increased in all the HA fractions with age after burial.

4) Hydrolyzable total- and sugar-carbon contents were high in the HA fractions of Yu 1 and decreased with age.

5) Changes of elementary composition, degree of humification and hydrolyzable total- and sugar-carbon contents were conspicuous from the Yu 1 to Yu 2 horizons, and less significant afterwards.

6) The 0%, C/O ratio and phenolic OH content did not show any consistent change with age after burial.     

Estimation of annual suspended sediment yield from a Japanese cypress (Chamaecyparis obtusa) plantation considering antecedent rainfalls

Japanese cypress (Chamaecyparis obtusa) is one of the most common plantation species in Japan. In most Japanese cypress plantations, closure of the forest canopy hinders understory growth because of insufficient management practices. Thus leaf litter barely covers the soil surface. Such plantations are vulnerable to surface erosion triggered by rainfalls, and could yield large amounts of suspended sediment (SS). However, few studies have investigated the annual SS yield. This study aimed to develop a modified model of SS yields, and to accurately estimate and characterize the annual SS yield from a Japanese cypress plantation. For this, hydrological surveys were conducted for 5 years, and stream water was sampled weekly as well as sequentially at 15–60 min intervals in each of 14 rain events in a small forested watershed of Japanese cypress. The root mean square error (RMSE) and the annual SS yield estimates were obtained using three different equations: the rating curve derived from instantaneous SS concentration versus stream discharge relationship (SSC − Q equation); the rating curve derived from cumulative SS yield versus cumulative specific discharge relationship (∑SS − ∑Q equation); and the multiple regression of cumulative SS yield expressed as functions of cumulative specific discharge and antecedent rainfalls (∑SS − ∑Q × AR equation). The ∑SS − ∑Q × AR equation is a modified model considering the effects of antecedent rain history on the SS yield. The parameters in each equation were determined by a nonlinear least square method. Of the three equations, the RMSE was the highest using the SSC − Q equation. Although the ∑SS − ∑Q equation and the ∑SS − ∑Q × AR equation gave similar RMSE values, the SS yields extrapolated by the ∑SS − ∑Q equation would be overestimated. Thus, the 5-year average of annual SS yield estimated by the ∑SS − ∑Q equation was three times larger than that estimated by the ∑SS − ∑Q × AR equation. These results indicate that the ∑SS − ∑Q × AR equation more accurately estimates the annual SS yield, compared with the other two equations. The results also suggest that antecedent rain history, as well as stream discharge, should be considered for appropriately estimating the annual SS yield. The annual SS yield estimated by the ∑SS − ∑Q × AR equation was the largest among 25 undisturbed forested watersheds, except for two watersheds dominated by sandstone. Our results suggest that the annual SS yield is greater from a Japanese cypress plantation under current management practices than from other undisturbed forests.     

Stand-scale transpiration estimates in a Moso bamboo forest: (I) Applicability of sap flux measurements

The applicability of sap flux (F_d) measurements to bamboo forests has not been studied. This study was undertaken to establish an optimal and effective design for stand-scale transpiration (E) estimates in a Moso bamboo forest. To this aim, we validated F_d measurements in Moso bamboos in a cut bamboo experiment. In addition, we analyzed how sample sizes affect the reliability of E estimates calculated from F_d and conducting culm area (A_{S_b}). In the cut bamboo experiments, we found that F_d measurement using a 10 mm probe was a valid means of determining the water-use behavior of a Moso bamboo, although a specific correction was needed. Furthermore, we calculated E from stand A_{S_b} (A_{S_stand}) and mean stand F_d (J_S). Employing Monte Carlo analysis, we examined potential errors associated with sample size in E, A_{S_stand}, and J_S using an original dataset with A_{S_b} and F_d measured for 40 and 16 individuals, respectively. Consequently, we determined the optimal sample size for both A_{S_stand} and J_S estimates as 11. The optimal sample sizes for J_S were almost the same under different vapor pressure deficit and soil moisture conditions. The optimal sample size for J_S at the study site was less than that of a coniferous plantation in the same region probably owing to small individual-to-individual variations in sap flux in the Moso bamboo forest. Our study concludes that sap flux measurements are an applicable technique for assessing water use in Moso bamboo forests.